WO2015157765A1 - Silane compounds and methods of using thereof - Google Patents
Silane compounds and methods of using thereof Download PDFInfo
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- WO2015157765A1 WO2015157765A1 PCT/US2015/025587 US2015025587W WO2015157765A1 WO 2015157765 A1 WO2015157765 A1 WO 2015157765A1 US 2015025587 W US2015025587 W US 2015025587W WO 2015157765 A1 WO2015157765 A1 WO 2015157765A1
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- unsubstituted
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 150000004756 silanes Chemical class 0.000 title abstract description 35
- -1 silane compound Chemical class 0.000 claims abstract description 161
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 125000003118 aryl group Chemical group 0.000 claims description 358
- 239000001257 hydrogen Substances 0.000 claims description 344
- 229910052739 hydrogen Inorganic materials 0.000 claims description 344
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 302
- 150000001875 compounds Chemical class 0.000 claims description 270
- 125000001072 heteroaryl group Chemical group 0.000 claims description 262
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 245
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 207
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 203
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 194
- 125000000217 alkyl group Chemical group 0.000 claims description 187
- 229910052736 halogen Inorganic materials 0.000 claims description 171
- 150000002367 halogens Chemical class 0.000 claims description 170
- 125000003545 alkoxy group Chemical group 0.000 claims description 155
- 125000003342 alkenyl group Chemical group 0.000 claims description 149
- 125000000304 alkynyl group Chemical group 0.000 claims description 149
- 125000001188 haloalkyl group Chemical group 0.000 claims description 133
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 98
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 96
- 150000003573 thiols Chemical class 0.000 claims description 96
- 125000004001 thioalkyl group Chemical group 0.000 claims description 89
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 78
- 125000004429 atom Chemical group 0.000 claims description 70
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 67
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 59
- 125000004122 cyclic group Chemical group 0.000 claims description 47
- 125000005842 heteroatom Chemical group 0.000 claims description 39
- 239000012491 analyte Substances 0.000 claims description 38
- 230000008859 change Effects 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 12
- 239000012038 nucleophile Substances 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 150000002118 epoxides Chemical group 0.000 claims description 3
- 230000000269 nucleophilic effect Effects 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 230000009919 sequestration Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 53
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 50
- 238000004020 luminiscence type Methods 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 abstract description 52
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 187
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 156
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 125
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 85
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 42
- 235000019439 ethyl acetate Nutrition 0.000 description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000741 silica gel Substances 0.000 description 31
- 229910002027 silica gel Inorganic materials 0.000 description 31
- 238000004296 chiral HPLC Methods 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 25
- 239000002904 solvent Substances 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 238000003818 flash chromatography Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 125000001424 substituent group Chemical group 0.000 description 20
- 238000006555 catalytic reaction Methods 0.000 description 19
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 17
- 238000000746 purification Methods 0.000 description 17
- LTVRSJBNXLZFGT-UHFFFAOYSA-N 2-silylethenone Chemical compound [SiH3]C=C=O LTVRSJBNXLZFGT-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000006862 quantum yield reaction Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000004820 halides Chemical class 0.000 description 15
- 238000006683 Mannich reaction Methods 0.000 description 14
- 125000000392 cycloalkenyl group Chemical group 0.000 description 14
- 230000003595 spectral effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 13
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 12
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 11
- 239000012230 colorless oil Substances 0.000 description 11
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000003480 eluent Substances 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 8
- 239000012267 brine Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 0 CCC*1C=C(C)C(C)C1 Chemical compound CCC*1C=C(C)C(C)C1 0.000 description 7
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000000707 stereoselective effect Effects 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- 150000003462 sulfoxides Chemical class 0.000 description 6
- LJCZNYWLQZZIOS-UHFFFAOYSA-N 2,2,2-trichlorethoxycarbonyl chloride Chemical compound ClC(=O)OCC(Cl)(Cl)Cl LJCZNYWLQZZIOS-UHFFFAOYSA-N 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000037361 pathway Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 229910015845 BBr3 Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000005595 deprotonation Effects 0.000 description 4
- 238000010537 deprotonation reaction Methods 0.000 description 4
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- QUTIPEXRXWCDRJ-UHFFFAOYSA-N dihydroxy(dinaphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](O)(C=3C4=CC=CC=C4C=CC=3)O)=CC=CC2=C1 QUTIPEXRXWCDRJ-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 125000000026 trimethylsilyl group Chemical class [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000020335 dealkylation Effects 0.000 description 3
- 238000006900 dealkylation reaction Methods 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 150000003840 hydrochlorides Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 3
- XBHPFCIWRHJDCP-UHFFFAOYSA-N (2-trimethylsilylphenyl) trifluoromethanesulfonate Chemical compound C[Si](C)(C)C1=CC=CC=C1OS(=O)(=O)C(F)(F)F XBHPFCIWRHJDCP-UHFFFAOYSA-N 0.000 description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 2
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 2
- VRVIOLMGIPZEFL-UHFFFAOYSA-N 13,13-dihydroxy-13-silapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene Chemical compound C1=CC=2C[Si](CC3=C(C2C=2C=CC=CC12)C1=CC=CC=C1C=C3)(O)O VRVIOLMGIPZEFL-UHFFFAOYSA-N 0.000 description 2
- QISLPEALMDRHHI-UHFFFAOYSA-N 13,13-dimethoxy-13-silapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene Chemical compound CO[Si]1(CC2=C(C3=C(C1)C=CC1=CC=CC=C13)C=1C=CC=CC1C=C2)OC QISLPEALMDRHHI-UHFFFAOYSA-N 0.000 description 2
- KDHFKMDVFWYSPT-UHFFFAOYSA-N 2-methyl-1-(2-methylnaphthalen-1-yl)naphthalene Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3C)=C(C)C=CC2=C1 KDHFKMDVFWYSPT-UHFFFAOYSA-N 0.000 description 2
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical class OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WOXKDUGGOYFFRN-IIBYNOLFSA-N tadalafil Chemical compound C1=C2OCOC2=CC([C@@H]2C3=C(C4=CC=CC=C4N3)C[C@H]3N2C(=O)CN(C3=O)C)=C1 WOXKDUGGOYFFRN-IIBYNOLFSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229960003048 vinblastine Drugs 0.000 description 1
- JXLYSJRDGCGARV-XQKSVPLYSA-N vincaleukoblastine Chemical compound C([C@@H](C[C@]1(C(=O)OC)C=2C(=CC3=C([C@]45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C)C=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 JXLYSJRDGCGARV-XQKSVPLYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
- C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
- C07D217/16—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Definitions
- the multistep synthesis of complex organic compounds can employ stereoselective synthetic steps to provide, for example, enantioenriched compositions of a desired stereoisomer.
- the synthesis of bioactive compounds such as Vinblastine, Lexapro, and Cialis can involve the stereoselective syntheses of arene rich triaryl- or diaryl- functionalities.
- stereoselective synthetic methodologies are known in the art, including stereoselective methods for the preparation of triaryl- and diaryl- methanes.
- many existing methods for preparing compounds in a stereoselective manner are inefficient (e.g., low yielding) and/or require the use of enantioenriched substrates.
- Improved stereoselective synthetic methodologies for preparing a variety of complex organic compounds, including triaryl- and diaryl- methanes, are needed.
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 4 , R 5 , and R 6 i.e., R 2 -R 6
- R 2’ , R 3’ , R 4’ , R 5’ , and R 6’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl
- R 7 and R 7’ are each independently chosen from H, OH, and halogen;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 and R 9 together with the atoms to which they are attached, form a 7-membered silacycle, R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both phenyl.
- R 8 and R 9 together with the atoms to which they are attached, form a 9-membered silacycle, R 1 , R 1’ , R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 8 and R 9 together with the atoms to which they are attached, form a 9-membered silacycle, R 1 and R 1’ are not both–CH 3 ; and R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both chosen from the moieties shown below.
- the compound can be defined by Formula II:
- the compound exhibits C 2 -symmetry.
- R 1 , R 1’ , R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 1 and R 1’ are not both–CH 3 ; and R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both chosen from the moieties shown below.
- the compound can be defined by Formula III:
- n and m are both 1 and the compound can be defined by Formula IIIa:
- R 1 , R 1’ , R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are as defined above with respect to Formula I.
- the compound can be defined by Formula IV:
- n, m, R 1 , R 1’ , R 3 , R 5 , R 3’ , and R 5’ are as defined above with respect to Formula I.
- n and m are both 1 and the compound can be defined by Formula IVa:
- R 1 , R 1’ , R 3 , R 5 , R 3’ , and R 5’ are as defined above with respect to Formula I.
- the compound can be defined by Formula V:
- n, m, R 1 , R 1’ , R 3 , and R 3’ are as defined above with respect to Formula I.
- n and m are both 1 and the compound can be defined by Formula Va:
- R 1 , R 1’ , R 3 , and R 3’ are as defined above with respect to Formula I.
- the compound can be defined by Formula VI:
- n, m, R 1 , R 1’ , R 5 , and R 5’ are as defined above with respect to Formula I.
- n and m are both 1 and the compound can be defined by Formula VIa:
- R 1 , R 1’ , R 5 , and R 5’ are as defined above with respect to Formula I.
- the compound can be defined by Formula VII:
- n and m are both 1 and the compound can be defined by Formula VIIa:
- R 1 , R 1’ , R 2 , and R 2’ are as defined above with respect to Formula I.
- the compound can be defined by Formula VIII:
- n, m, R 1 , and R 1’ are as defined above with respect to Formula I.
- n and m are both 1 and the compound can be defined by Formula VIIIa:
- R 1 and R 1’ are as defined above with respect to Formula I.
- the compound can be one of the following:
- the compound can be defined by Formula IX: R 5 R 5'
- n, m, R 1 , R 1’ , R 2 , R 3 , R 5 , R 2’ , R 3’ , R 5’ , R 8 , and R 9 are as defined above with respect to Formula I.
- m is 0.
- R 9 is substituted or unsubstituted aryl.
- m is 0 and R 9 is substituted or unsubstituted aryl.
- R 8 is chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- the compound can be defined by Formula X:
- n, m, R 1 , R 1’ , R 3 , R 5 , R 3’ , R 5’ , R 8 , and R 9 are as defined above with respect to Formula I.
- m is 0.
- R 9 is substituted or unsubstituted aryl.
- m is 0 and R 9 is substituted or unsubstituted aryl.
- R 8 is chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- the compound can be defined by Formula XI: XI
- n, m, R 1 , R 1’ , R 3 , R 3’ , R 8 , and R 9 are as defined above with respect to Formula I.
- m is 0.
- R 9 is substituted or unsubstituted aryl.
- m is 0 and R 9 is substituted or unsubstituted aryl.
- R 8 is chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- the compound can be defined by Formula XII:
- n, m, R 1 , R 1’ , R 5 , R 5’ , R 8 , and R 9 are as defined above with respect to Formula I.
- m is 0.
- R 9 is substituted or unsubstituted aryl.
- m is 0 and R 9 is substituted or unsubstituted aryl.
- R 8 is chosen from the moieties shown below ;
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- the compound can be defined by Formula XIII:
- n, m, R 1 , R 1’ , R 2 , R 2’ , R 8 , and R 9 are as defined above with respect to Formula I.
- m is 0.
- R 9 is substituted or unsubstituted aryl.
- m is 0 and R 9 is substituted or unsubstituted aryl.
- R 8 is chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- the compound can be defined by Formula XIV: XIV
- n, m, R 1 , R 1’ , R 8 , and R 9 are as defined above with respect to Formula I.
- m is 0.
- R 9 is substituted or unsubstituted aryl.
- m is 0 and R 9 is substituted or unsubstituted aryl.
- R 8 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- the com ound can be one of the followin :
- n 0 or 1;
- R 10 and R 10’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 12’ , R 13’ , R 14’ , R 15’ , R 16’ , and R 17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsub
- R 18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- the compound in some examples of Formula XV, can be defined by Formula XVa:
- R 10 , R 10’ , R 12 , R 13 , R 17 , R 12’ , R 13’ , R 17’ , and R 18 are as defined above with respect to Formula XV.
- the compound in some examples of Formula XVa, can be defined by Formula XVb: R 17' R 17
- n, R 10 , R 10’ , R 17 , R 17’ , and R 18 are as defined above with respect to Formula XV.
- the compound in some examples of Formula XVb, can be defined by the formula:
- the compound in some examples of Formula XVa, can be defined by Formula XVc: R 17 R 17
- n, R 10 , R 10’ , R 12 , R 13 , R 17 , R 17’ , and R 18 are as defined above with respect to Formula XV.
- the compound can be defined by Formula XVd:
- n, R 10 , R 10’ , R 17 , R 17’ , and R 18 are as defined above with respect to Formula XV.
- the compounds described above can be in a complex with a suitable solvent, such as diethyl ether.
- a suitable solvent such as diethyl ether.
- the compounds can be in a 2:1 complex with diethyl ether.
- the silane compounds provided herein can be used as organocatalysts.
- the silane compounds described herein can be used to catalyze a nucleophilic conjugate addition reaction in which a first organic species comprising a nitroalkene reacts with a second organic species comprising a nucleophile to provide a product.
- the silane compounds described herein can also be used to catalyze an acyl-Mannich type reaction in which a first organic species comprising an amine reacts with a second organic species comprising a carbonyl containing compound to provide a product.
- Methods of using the silane compounds described herein as catalysts can involve contacting a first organic species and a second organic species with a catalytically effective amount of a silane compound or a catalyst composition comprising a silane compound under conditions effective to form the desired product.
- the product can preferably be enantioenriched.
- silane compounds described herein can also be used as sensors for analytes.
- suitable analytes include, for example, anions and chiral compounds.
- the methods comprise contacting the sample comprising an analyte with a silane compound described herein; and evaluating an optical property of the silane compound to detect, identify, or quantify the analyte.
- Figure 1 displays the chiral HPLC of 9a formed using 8-TMS and 20 mol% R-3.
- Figure 2 displays the chiral HPLC of 9a formed using 8-TBS and 20 mol% R-3.
- Figure 3 displays the chiral HPLC of 9a formed using 8-TIPS and 20 mol% R-3.
- Figure 4 displays the chiral HPLC of 9a formed using 8-TIPS and 100 mol% R-3.
- Figure 5 displays the chiral HPLC of 2,2,2-trichloroethyl 5-bromo-1-(1-methoxy-2- methyl-1-oxopropan-2-yl)isoquinoline-2(1H)-carboxylate (9b) formed using 8-TIPS and 20 mol % R-3.
- Figure 6 displays the chiral HPLC of 9b formed using 8-TBS, 20 mol% R-3.
- Figure 7 displays the chiral HPLC of 2,2,2-trichloroethyl 5-chloro-1-(1-methoxy-2- methyl-1-oxopropan-2-yl)isoquinoline-2(1H)-carboxylate (9c) formed using 8-TIPS, 20 mol % R-3.
- Figure 8 displays the chiral HPLC of 9c formed using 8-TBS and 20 mol% R-3.
- Figure 9 displays the chiral HPLC of 2,2,2-trichloroethyl 1-(1-methoxy-2-methyl-1 - oxopropan-2-yl)-5-nitroisoquinoline-2(1H)-carboxylate (9d) formed using 8-TIPS, 20 mol % R-3.
- Figure 10 displays the chiral HPLC of 9d formed using 8-TBS, 20 mol% R-3.
- Figure 11 displays the chiral HPLC of racemic mixture of 9a.
- Figure 12 displays the chiral HPLC of racemic mixture of 9b.
- Figure 13 displays the chiral HPLC of racemic mixture of 9c.
- Figure 14 displays the chiral HPLC of racemic mixture of 9d.
- Figure 15 displays the chiral HPLC of an enantiopure Bis(TMS) derivative of Silanediol R-3.
- Figure 16 displays the chiral HPLC of racemic Bis(TMS) derivative of Silanediol R- 3.
- Figure 17 displays the chiral HPLC of S2 formed using S1, 20 mol% R-3.
- Figure 18 displays the chiral HPLC of racemic S2.
- Figure 19 displays the ORTEP representation of bis-trimethylsilyl protected (R)-3.
- Figure 20 displays the 1 H NMR spectra of (R)-3 with varying equivalents of tetrabutylammonium chloride (TBACl). The–OH chemical shifts are marked with a circle.
- Figure 21 displays the ORTEP representation of an ion-pair between achiral silanediol 1 and the HCl salt of isoquinoline.
- the O1-Cl and N-Cl distances are 2.12 ⁇ and 2.32 ⁇ respectively, indicative of moderately strong hydrogen bonds (Steiner T, Angew. Chem. Int. Ed. 2002, 41, 48-76).
- the O2-Cl bond is longer, with a distance of 4.47 ⁇ .
- Figure 22 displays the crystal structure of H 2 O complex of ( ⁇ )-21b.
- Figure 23 displays the crystal structure of bis-TMS derivative of (R)-22.
- Figure 24 displays the crystal structure of a trimer derived from (R)-22b. The anisotropic displacement parameters are drawn at the 50% probability level.
- Figure 25 displays the pK a s and anion binding constants for representative silanediols.
- Figure 26 illustrates the 1 H NMR binding titration of silanediol (R)-22b with n-
- Figure 27 illustrates the Job’s plot analysis of (R)-22b and n-Bu 4 NCl in CDCl 3 .
- Figure 28 displays the crystal structure of ion pair between di(naphthalen-1- yl)silanediol and the HCl salt of isoquinoline.
- Figure 29 displays the proposed reaction pathway for silanediol-catalyzed N-acyl Mannich reaction of isoquinolines.
- Ranges can be expressed herein as from“about” one particular value, and/or to “about” another particular value. By“about” is meant within 5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent“about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
- the term“substituted” is contemplated to include all permissible substituents of organic compounds.
- the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds.
- Illustrative substituents include, for example, those described below.
- the permissible substituents can be one or more and the same or different for appropriate organic compounds.
- heteroatoms present in a compound or moiety, such as nitrogen can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valency of the heteroatom.
- substitution or“substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.
- Z 1 ,”“Z 2 ,”“Z 3 ,” and“Z 4 ” are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.
- aliphatic refers to a non-aromatic hydrocarbon group and includes branched and unbranched, alkyl, alkenyl, or alkynyl groups.
- alkyl as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, for example 1 to 3, 1 to 4, 1 to 5, 1 to 6, 1 to 7, 1 to 8, 1 to 9, 1 to 10, or 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like.
- the alkyl group can also be substituted or unsubstituted.
- the alkyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below.
- alkyl is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group.
- halogenated alkyl specifically refers to an alkyl group that is substituted with one or more halides (halogens; e.g., fluorine, chlorine, bromine, or iodine).
- alkoxyalkyl specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below.
- alkylamino specifically refers to an alkyl group that is substituted with one or more amino groups, as described below, and the like.
- “alkyl” is used in one instance and a specific term such as“alkylalcohol” is used in another, it is not meant to imply that the term“alkyl” does not also refer to specific terms such as“alkylalcohol” and the like.
- cycloalkyl refers to both unsubstituted and substituted cycloalkyl moieties
- the substituted moieties can, in addition, be specifically identified herein; for example, a particular substituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.”
- a substituted alkoxy can be specifically referred to as, e.g., a“halogenated alkoxy”
- a particular substituted alkenyl can be, e.g., an“alkenylalcohol,” and the like.
- the practice of using a general term, such as“cycloalkyl,” and a specific term, such as “alkylcycloalkyl,” is not meant to imply that the general term does not also include the specific term.
- alkoxy as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an“alkoxy” group can be defined as—OZ 1 where Z 1 is alkyl as defined above.
- alkenyl as used herein is a hydrocarbon group of from 2 to 24 carbon atoms, for example, 2 to 5, 2 to 10, 2 to 15, or 2 to 20 carbon atoms, with a structural formula containing at least one carbon-carbon double bond.
- the alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below.
- groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described
- alkynyl as used herein is a hydrocarbon group of 2 to 24 carbon atoms, for example 2 to 5, 2 to 10, 2 to 15, or 2 to 20 carbon atoms, with a structural formula containing at least one carbon-carbon triple bond.
- the alkynyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below.
- groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as
- aryl as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl,
- heteroaryl is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
- non-heteroaryl which is included in the term“aryl,” defines a group that contains an aromatic group that does not contain a heteroatom. The aryl or heteroaryl group can be substituted or unsubstituted.
- the aryl or heteroaryl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
- the term“biaryl” is a specific type of aryl group and is included in the definition of aryl. Biaryl refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.
- cycloalkyl as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms.
- examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
- heterocycloalkyl is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
- the cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted.
- the cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
- cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like.
- heterocycloalkenyl is a type of cycloalkenyl group as defined above, and is included within the meaning of the term“cycloalkenyl,” where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
- the cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted.
- the cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
- cyclic group is used herein to refer to either aryl groups, non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both. Cyclic groups have one or more ring systems that can be substituted or unsubstituted. A cyclic group can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups.
- carbonyl as used herein is represented by the formula–C(O)Z 1 where Z 1 can be a hydrogen, hydroxyl, alkoxy, alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- Z 1 can be a hydrogen, hydroxyl, alkoxy, alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- aldehyde as used herein is represented by the formula—C(O)H.
- amine or“amino” as used herein are represented by the formula— NZ 1 Z 2 , where Z 1 and Z 2 can each be substitution group as described herein, such as hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- “Amido” is —C(O)NZ 1 Z 2 .
- esters as used herein is represented by the formula—OC(O)Z 1 or —C(O)OZ 1 , where Z 1 can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- ether as used herein is represented by the formula Z 1 OZ 2 , where Z 1 and Z 2 can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- ketone as used herein is represented by the formula Z 1 C(O)Z 2 , where Z 1 and Z 2 can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- halide or“halogen” as used herein refers to the fluorine, chlorine, bromine, and iodine.
- nitro as used herein is represented by the formula—NO 2 .
- silica as used herein is represented by the formula—SiZ 1 Z 2 Z 3 , where Z 1 , Z 2 , and Z 3 can be, independently, hydrogen, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- sulfonyl is used herein to refer to the sulfo-oxo group represented by the formula—S(O) 2 Z 1 , where Z 1 can be hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
- R 1 is a straight chain alkyl group
- one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an amine group, an alkyl group, a haiide, and the like.
- a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group.
- an alkyl group comprising an amino group the amino group can be incorporated within the backbone of the alkyl group.
- the amino group can be attached to the backbone of the alkyl group.
- the nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.
- EDG electron donating group
- substituents e.g., atoms or functional groups
- an electron donating group can, for example, make the benzene more likely to participate in electrophilic substitution reactions.
- electron donating groups include, but are not limited to, primary, secondary and tertiary amines; hydroxy groups; amides; alkoxy groups; alkyl groups; and aryl groups.
- EWG electron withdrawing group
- substituents e.g., atoms or functional groups
- EWG electron withdrawing group
- substituents e.g., atoms or functional groups
- electron withdrawing group can, for example, make electrophilic aromatic substitution reactions slower and more complex.
- electron withdrawing groups can also determine the positions (relative to themselves) on the benzene ring where substitutions can take place.
- electron withdrawing groups include, but are not limited to, nitro, quaternary amines, trihalides (e.g., -CFV), cyano, sulfonates, carboxylic acids, esters, aldehydes, and ketones.
- a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible stereoisomer or mixture of stereoisomer (e.g., each enantiomer, each diastereomer, each meso compound, a racemic mixture, or scalemic mixture).
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted al
- R 7 and R 7’ are each independently chosen from H, OH, and halogen;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 and R 9 together with the atoms to which they are attached, form a 7-membered silacycle, R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both phenyl.
- R 8 and R 9 together with the atoms to which they are attached, form a 9-membered silacycle, R 1 , R 1’ , R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 8 and R 9 together with the atoms to which they are attached, form a 9-membered silacycle, R 1 and R 1’ are not both–CH 3 ; and R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both chosen from the moieties shown below.
- n is 0. In some examples of Formula I, m is 0. In some examples of Formula I, n and m are 0. In some examples of Formula I, n is 1. In some examples of Formula I, m is 1. In some examples of Formula I, at least one of n and m is 1. In some examples of Formula I, n and m are 1. In some examples of Formula I, n is 1 and m is 0.
- R 1 and R 1’ are the same. In some examples of Formula I, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula I, R 1 and R 1’ are both hydrogen. In some examples of Formula I, R 1 and R 1’ are both–CH 3 .
- R 2 and R 2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 2 and R 2’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 2 and R 2’ are independently substituted or unsubstituted alkylaryl.
- R 2 and R 2’ are independently substituted or unsubstituted aryl.
- R 2 and R 2’ are independently chosen from the moieties shown below ;
- R 2 and R 2’ are independently substituted or unsubstituted phenyl.
- R 2 and R 2’ are the same. In some examples of Formula I, R 2 and R 2’ are both hydrogen.
- R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 3 and R 3’ are independently substituted or unsubstituted alkylaryl.
- R 3 and R 3’ are independently substituted or unsubstituted aryl.
- R 3 and R 3’ are independently chosen from the moieties shown below
- R 3 and R 3’ are independently substituted or unsubstituted phenyl.
- R 3 and R 3’ are the same. In some examples of Formula I, R 3 and R 3’ are both hydrogen. In some examples of Formula I, R 4 and R 4’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula I, R 4 and R 4’ are the same. In certain examples of Formula I, R 4 and R 4’ are both hydrogen.
- R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are independently substituted or unsubstituted alkylaryl.
- R 5 and R 5’ are independently substituted or unsubstituted aryl.
- R 5 and R 5’ are independently chosen from the moieties shown below
- R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 5 and R 5’ are the same. In some examples of Formula I, R 5 and R 5’ are both hydrogen.
- R 3 and R 3’ are the same, and R 5 and R 5’ are the same.
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula I, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted aryl.
- R 3 , R 3’ , R 5 and R 5’ are chosen from the moieties shown below
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 3 and R 3’ are both hydrogen, and R 5 and R 5’ are the same. In some examples of Formula I, R 3 and R 3’ are the same and R 5 and R 5’ are both hydrogen. In some examples of Formula I, R 3 , R 3’ , R 5 and R 5’ are all the same. In some examples of Formula I, R 3 , R 3’ , R 5 , and R 5’ are all hydrogen.
- R 6 and R 6’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula I, R 6 and R 6’ are the same. In certain examples of Formula I, R 6 and R 6’ are both hydrogen.
- R 7 and R 7’ are the same. In some examples of Formula I, R 7 and R 7’ are both hydrogen.
- R 4 , R 6 , R 4’ , and R 6’ are the same. In some examples of Formula I, R 4 , R 6 , R 4’ , and R 6’ are all hydrogen. In some examples of Formula I, R 4 , R 7 , R 4’ , and R 7’ are the same. In some examples of Formula I, R 4 , R 7 , R 4’ , and R 7’ are all hydrogen. In some examples of Formula I, R 6 , R 7 , R 6’ , and R 7’ are the same. In some examples of Formula I, R 6 , R 7 , R 6’ , and R 7’ are all hydrogen.
- R 4 , R 6 , R 7 , R 4’ , R 6’ , and R 7’ are the same. In some examples of Formula I, R 4 , R 6 , R 7 , R 4’ , R 6’ , and R 7’ are all hydrogen.
- R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula I, R 8 and R 9 are substituted or unsubstituted alkylaryl. In certain examples of Formula I, R 8 and R 9 are substituted or unsubstituted aryl.
- R 8 and R 9 are independently chosen from the moieties shown below
- R 8 and R 9 are independently substituted or unsubstituted phenyl.
- R 8 and R 9 together with the atoms to which they are attached, form a 7-9 membered silacycle, and the compound can be defined by Formula II:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted al
- R 7 and R 7’ are each independently chosen from H, OH, and halogen;
- the compound exhibits C 2 -symmetry.
- R 1 , R 1’ , R 2 -R 7 and R 2’ -R 7’ are not all H.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 , R 1’ , R 3 -R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl.
- R 1 , R 1’ , R 3 - R 7 and R 3’ -R 7’ are not all H and R 2 and R 2’ are not both chosen from the moieties shown below.
- n is 0. In some examples of Formula II, m is 0. In some examples of Formula II, n and m are 0. In some examples of Formula II, n is 1. In some examples of Formula II, m is 1. In some examples of Formula II, at least one of n and m is 1. In some examples of Formula II, n and m are 1.
- R 1 and R 1’ are the same. In some examples of Formula II, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula II, R 1 and R 1’ are both hydrogen. In some examples of Formula II, R 1 and R 1’ are both–CH 3 .
- R 2 and R 2’ are the same.
- R 2 and R 2’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 2 and R 2’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R 2 and R 2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R 2 and R 2’ are substituted or unsubstituted aryl.
- R 2 and R 2’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 2 and R 2’ are substituted or unsubstituted phenyl.
- R 3 and R 3’ are the same.
- R 3 and R 3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 3 and R 3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R 3 and R 3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R 3 and R 3’ are substituted or unsubstituted aryl.
- R 3 and R 3’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 3 and R 3’ are substituted or unsubstituted phenyl.
- R 4 and R 4’ are the same. In some examples of Formula II, R 4 and R 4’ are both chosen from hydrogen, hydroxy, and halogen. In certain examples of Formula II, R 4 and R 4’ are both hydrogen.
- R 5 and R 5’ are the same.
- R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R 5 and R 5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R 5 and R 5’ are substituted or unsubstituted aryl.
- R 5 and R 5’ are chosen from the moieties shown below ;
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 3 and R 3’ are the same, and R 5 and R 5’ are the same.
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted aryl.
- R 3 , R 3’ , R 5 and R 5’ are chosen from the moieties shown below
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 6 and R 6’ are the same. In some examples of Formula II, R 6 and R 6’ are both chosen from hydrogen, hydroxy, and halogen. In certain examples of Formula II, R 6 and R 6’ are both hydrogen.
- R 7 and R 7’ are the same. In some examples of Formula II, R 7 and R 7’ are both hydrogen. In some examples of Formula II, R 4 , R 6 , R 4’ , and R 6’ are the same. In some examples of Formula II, R 4 , R 6 , R 4’ , and R 6’ are all hydrogen. In some examples of Formula II, R 4 , R 7 , R 4’ , and R 7’ are the same. In some examples of Formula II, R 4 , R 7 , R 4’ , and R 7’ are all hydrogen. In some examples of Formula II, R 6 , R 7 , R 6’ , and R 7’ are the same. In some examples of Formula II, R 6 , R 7 , R 6’ , and R 7’ are all hydrogen.
- R 4 , R 6 , R 7 , R 4’ , R 6’ , and R 7’ are the same.
- R 4 , R 6 , R 7 , R 4’ , R 6’ and R 7’ are all hydrogen, and the compound can be defined by Formula III:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R 2 and R 3 , and/or R 2’ and R 3’ , together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
- n is 0.
- m is 0.
- n and m are 0.
- n is 1.
- m is 1.
- n and m are both 1.
- the compound of Formula III can be defined by Formula IIIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R 2 and R 3 , and/or R 2’ and R 3’ , together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms.
- R 1 , R 1’ , R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are not all H. In some examples of Formula IIIa, when R 1 and R 1’ are both–CH 3 , R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are not all H.
- R 2 and R 2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted
- R 1 , R 1’ , R 3 , R 5 , R 3’ , and R 5’ are all H, R 2 and R 2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl.
- R 1 , R 1’ , R 3 , R 5 , R 3’ , and R 5’ are all H, R 2 and R 2’ are not both chosen from the moieties shown below.
- the compound exhibits C 2 - symmetry.
- R 1 and R 1’ are the same. In some examples of Formula III and Formula IIIa, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula III and Formula IIIa, R 1 and R 1’ are both hydrogen. In some examples of Formula III and Formula IIIa, R 1 and R 1’ are both–CH 3 .
- R 2 and R 2’ are the same. In some examples of Formula III and Formula IIIa, R 2 and R 2’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 2 and R 2’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 2 and R 2’ are substituted or unsubstituted alkylaryl.
- R 2 and R 2’ are substituted or unsubstituted aryl.
- R 2 and R 2’ are chosen from the moieties shown below ;
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 2 and R 2’ are substituted or unsubstituted phenyl.
- R 3 and R 3’ are the same. In some examples of Formula III and Formula IIIa, R 3 and R 3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 3 and R 3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 3 and R 3’ are substituted or unsubstituted alkylaryl.
- R 3 and R 3’ are substituted or unsubstituted aryl.
- R 3 and R 3’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 3 and R 3’ are substituted or unsubstituted phenyl.
- R 5 and R 5’ are the same.
- R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula III and Formula IIIa, R 5 and R 5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula III and Formula IIIa, R 5 and R 5’ are substituted or unsubstituted aryl.
- R 5 and R 5’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 3 and R 3’ are the same, and R 5 and R 5’ are the same.
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula III and Formula IIIa, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted aryl.
- R 3 , R 3’ , R 5 and R 5’ are chosen from the moieties shown below ;
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 2 , R 4 , R 6 , R 7 , R 2’ , R 4’ , R 6’ and R 7’ are all hydrogen, and the compound can be defined by Formula IV:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 , R 5 , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0.
- m is 0.
- n and m are 0.
- n is 1.
- m is 1.
- at least one of n and m is 1.
- n and m are both 1.
- the compound of Formula IV can be defined by Formula IVa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 , R 5 , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 , R 1’ , R 3 , R 5 , R 3’ , and R 5’ are not all H.
- R 1 and R 1’ are both–CH 3 , R 3 , R 5 , R 3’ , and R 5’ are not all H.
- the compound exhibits C 2 - symmetry.
- R 1 and R 1’ are the same. In some examples of Formula IV and Formula IVa, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula IV and Formula IVa, R 1 and R 1’ are both hydrogen. In some examples of Formula IV and Formula IVa, R 1 and R 1’ are both–CH 3 .
- R 3 and R 3’ are the same.
- R 3 and R 3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 3 and R 3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IV and Formula IVa, R 3 and R 3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IV and Formula IVa, R 3 and R 3’ are substituted or unsubstituted aryl.
- R 3 and R 3’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 3 and R 3’ are substituted or unsubstituted phenyl.
- R 5 and R 5’ are the same.
- R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 5 and R 5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- R 5 and R 5’ are substituted or unsubstituted aryl.
- R 5 and R 5’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- R 5 and R 5’ are wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 5 and R 5’ are substituted or unsubstituted phenyl.
- R 3 and R 3’ are the same, and R 5 and R 5’ are the same.
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- R 3 , R 3’ , R 5 and R 5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IV and Formula IVa, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted aryl.
- R 3 , R 3’ , R 5 and R 5’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 3 , R 3’ , R 5 and R 5’ are
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- R 3 , R 3’ , R 5 and R 5’ are
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted phenyl.
- the compound can be defined by the formula:
- the compound can be defined by the formula:
- R 2 , R 4 , R 5 , R 6 , R 7 , R 2’ , R 4’ , R 5’ , R 6’ and R 7’ are all hydrogen, and the compound can be defined by Formula V:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 and R 3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula V, m is 0. In some examples of Formula V, n and m are 0. In some examples of Formula V, n is 1. In some examples of Formula V, m is 1.
- n and m are both 1.
- the compound of Formula V can be defined by Formula Va:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 and R 3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted hetero
- R 1 , R 1’ , R 3 , and R 3’ are not all H.
- R 1 and R 1’ are both–CH 3
- R 3 and R 3’ are not both H.
- the compound exhibits C 2 - symmetry.
- R 1 and R 1’ are the same. In some examples of Formula V and Formula Va, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula V and Formula Va, R 1 and R 1’ are both hydrogen. In some examples of Formula V and Formula Va, R 1 and R 1’ are both–CH 3 .
- R 3 and R 3’ are the same. In some examples of Formula V and Formula Va, R 3 and R 3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 3 and R 3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 3 and R 3’ are substituted or unsubstituted alkylaryl.
- R 3 and R 3’ are substituted or unsubstituted aryl.
- R 3 and R 3’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 3 and R 3’ are
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- R 3 and R 3’ are
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 3 and R 3’ are substituted or unsubstituted phenyl.
- the com ound can be defined by the formula:
- the com ound can be defined by the formula:
- R 2 , R 3 , R 4 , R 6 , R 7 , R 2’ , R 3’ , R 4’ , R 6’ and R 7’ are all hydrogen, and the compound can be defined by Formula VI: R 5'
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 5 and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula VI, m is 0. In some examples of Formula VI, n and m are 0. In some examples of Formula VI, n is 1. In some examples of Formula VI, m is 1.
- n and m are both 1.
- the compound of Formula VI can be defined by Formula VIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 5 and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 , R 1’ , R 5 , and R 5’ are not all H.
- R 1 and R 1’ are both–CH 3
- R 3 and R 3’ R 5’ are not both H.
- the compound exhibits C 2 - symmetry.
- R 1 and R 1’ are the same. In some examples of Formula VI and Formula VIa, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula VI and Formula VIa, R 1 and R 1’ are both hydrogen. In some examples of Formula VI and Formula VIa, R 1 and R 1’ are both–CH3.
- R 5 and R 5’ are the same. In some examples of Formula VI and Formula VIa, R 5 and R 5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 5 and R 5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- R 5 and R 5’ are substituted or unsubstituted aryl.
- R 5 and R 5’ are chosen from the moieties shown below ; wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- R 5 and R 5’ are examples of Formula VI and Formula VIa, R 5 and R 5’ are examples of Formula VI and Formula VIa, R 5 and R 5’ are examples of Formula VI and Formula VIa, R 5 and R 5’ are examples of Formula VI and Formula VIa, R 5 and R 5’ are
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 5 and R 5’ are substituted or unsubstituted phenyl.
- the com ound can be defined be the formula:
- the compound in some examples of Formula VIa, can be defined be the formula: 3 .
- R 3 , R 4 , R 5 , R 6 , R 7 , R 3’ , R 4’ , R 5’ , R 6’ and R 7’ are all hydrogen, and the compound can be defined by Formula VII:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 and R 2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- n is 0.
- m is 0.
- n and m are 0.
- n is 1.
- m is 1.
- at least one of n and m is 1.
- n and m are both 1.
- the compound of Formula VII can be defined by Formula VIIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 and R 2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 , R 1’ , R 2 , and R 2’ are not all H.
- R 1 and R 1’ are both–CH 3
- R 2 and R 2’ are not both H.
- R 1 and R 1’ are both H
- R 2 and R 2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkyl
- R 1 and R 1’ when R 1 and R 1’ are both H, R 2 and R 2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl. In some examples of Formula VIIa, when R 1 and R 1’ are both H, R 2 and R 2’ are not both chosen from the moieties shown below.
- the compound exhibits C 2 - symmetry.
- R 1 and R 1’ are the same. In some examples of Formula VII and Formula VIIa, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula VII and Formula VIIa, R 1 and R 1’ are both hydrogen. In some examples of Formula VII and Formula VIIa, R 1 and R 1’ are both–CH 3 .
- R 2 and R 2’ are the same. In some examples of Formula VII and Formula VIIa, R 2 and R 2’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 2 and R 2’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 2 and R 2’ are substituted or unsubstituted alkylaryl.
- R 2 and R 2’ are substituted or unsubstituted aryl.
- R 2 and R 2’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- R 2 and R 2’ are examples of Formula VII and Formula VIIa, R 2 and R 2’ are examples of Formula VII and Formula VIIa, R 2 and R 2’ are examples of Formula VII and Formula VIIa, R 2 and R 2’ are examples of Formula VII and Formula VIIa, R 2 and R 2’ are examples of Formula VII and Formula VIIa, R 2 and R 2’ are examples of Formula VII and Formula VIIa, R 2 and R 2’ are
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 2 and R 2’ are substituted or unsubstituted phenyl.
- R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 2’ , R 3’ , R 4’ , R 5’ , R 6’ and R 7’ are all hydrogen, and the compound can be defined by Formula VIII:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl.
- n is 0.
- m is 0.
- n and m are 0.
- n is 1.
- m is 1.
- at least one of n and m is 1.
- n and m are both 1.
- the compound of Formula VIII can be defined by Formula VIIIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl.
- the compound exhibits C 2 - symmetry.
- R 1 and R 1’ are the same. In some examples of Formula VIII and Formula VIIIa, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula VIII and Formula VIIIa, R 1 and R 1’ are both–CH 3 . In some examples of Formula VIII, R 1 and R 1’ are both hydrogen.
- R 1 and R 1’ are both hydrogen, and the compound can be defined by the form l
- R 1 and R 1’ are both methoxy, and the compound can be defined by the f rm l
- R 1 and R 1’ are both hydrogen, and the compound is a complex with an ether. In some examples of Formula VIIIa, R 1 and R 1’ are both hydrogen, and the compound is a complex with a diethyl ether. In some examples of Formula VIIIa, R 1 and R 1’ are both hydrogen, and the compound is a 2:1 complex with a diethyl ether.
- the compound can be defined by Formula IX:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R 2 and R 3
- R 2’ and R 3’ , or R 2’ and R 9 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula IX, m is 0. In some examples of Formula IX, n is 1. In some examples of Formula IX, m is 1. In some examples of Formula IX, at least one of n and m is 1. In some examples of Formula IX, n and m are both 1.
- n and m are both 0.
- the compound of Formula IX can be defined by Formula IXa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R 2 and R 3 , R 2’ and R 3’ , or R 2’ and R 9 , together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n 1 and m is 0.
- the compound of Formula IX can be defined by Formula IXb:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 , R 3 , R 5 , R 2’ , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R 2 and R 3
- R 2’ and R 3’ , or R 2’ and R 9 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;.
- Formula IXa, and Formula IXb, R 1 and R 1’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula IX, Formula IXa, and Formula IXb, R 1 and R 1’ are both hydrogen. In some examples of Formula IX, Formula IXa, and Formula IXb, R 1 and R 1’ are both–CH 3 .
- Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are substituted or unsubstituted aryl.
- Formula IXa In some examples of Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are substituted or unsubstituted phenyl.
- Formula IXa, and Formula IXb, R 2 and R 2’ are the same. In certain examples of Formula IX, Formula IXa, and Formula IXb, R 2 and R 2’ are hydrogen.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are substituted or unsubstituted alkylaryl.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are substituted or unsubstituted aryl.
- Formula IX In some examples of Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are substituted or unsubstituted phenyl.
- Formula IXa, and Formula IXb, R 3 and R 3’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are hydrogen.
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are substituted or unsubstituted aryl.
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- EDG represents an electron donating group
- EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are substituted or unsubstituted phenyl.
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are the same.
- Formula IX, Formula IXa, and Formula IXb, R 5 and R 5’ are hydrogen.
- Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted aryl.
- Formula IXa In some examples of Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 and R 5’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted phenyl.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are the same, and R 5 and R 5’ are the same.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are hydrogen, and R 5 and R 5’ are the same.
- Formula IX, Formula IXa, and Formula IXb, R 3 and R 3’ are the same, and R 5 and R 5’ are hydrogen.
- Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 , and R 5’ are the same.
- Formula IX, Formula IXa, and Formula IXb, R 3 , R 3’ , R 5 , and R 5’ are the hydrogen.
- Formula IX, Formula IXa, and Formula IXb, R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
- Formula IX, Formula IXa, and Formula IXb, R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula IX, Formula IXa, and Formula IXb, R 8 and R 9 are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R 8 and R 9 are substituted or unsubstituted aryl.
- Formula IXa Formula IXa, and Formula IXb, R 8 and R 9 are independently cho n fr m h m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula IX, Formula IXa, and Formula IXb, R 8 and R 9 are substituted or unsubstituted phenyl.
- the compound can be defined by Formula X:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 , R 5 , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula X, m is 0. In some examples of Formula X, n is 1. In some examples of Formula X, m is 1. In some examples of Formula X, at least one of n and m is 1. In some examples of Formula X, n and m are both 1.
- n and m are both 0.
- the compound of Formula X can be defined by Formula Xa: R 5'
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 , R 5 , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 , R 5 , R 3’ , and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula X, Formula Xa, and Formula Xb, R 1 and R 1’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula X, Formula Xa, and Formula Xb, R 1 and R 1’ are both hydrogen. In some examples of Formula X, Formula Xa, and Formula Xb, R 1 and R 1’ are both–CH 3 .
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are substituted or unsubstituted alkylaryl.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are substituted or unsubstituted aryl.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are substituted or unsubstituted phenyl.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are hydrogen.
- Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are substituted or unsubstituted aryl.
- Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are substituted or unsubstituted phenyl.
- Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R 5 and R 5’ are hydrogen.
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted aryl.
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 and R 5’ are chosen from h m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 and R 5’ are substituted or unsubstituted phenyl.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are the same, and R 5 and R 5’ are the same.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are hydrogen, and R 5 and R 5’ are the same.
- Formula X, Formula Xa, and Formula Xb, R 3 and R 3’ are the same, and R 5 and R 5’ are hydrogen.
- Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 , and R 5’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R 3 , R 3’ , R 5 , and R 5’ are the hydrogen.
- Formula X, Formula Xa, and Formula Xb, R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
- Formula X, Formula Xa, and Formula Xb, R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula X, Formula Xa, and Formula Xb, R 8 and R 9 are substituted or unsubstituted alkylaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R 8 and R 9 are substituted or unsubstituted aryl.
- Formula X In some examples of Formula X, Formula Xa, and Formula Xb, R 8 and R 9 are independently chosen from the moieties shown below ;
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula X, Formula Xa, and Formula Xb, R 8 and R 9 are substituted or unsubstituted phenyl.
- the compound can be defined by Formula XI:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 and R 3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XI, m is 0. In some examples of Formula XI, n is 1. In some examples of Formula XI, m is 1. In some examples of Formula XI, at least one of n and m is 1. In some examples of Formula XI, n and m are both 1.
- n and m are both 0.
- the compound of Formula XI can be defined by Formula XIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 and R 3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n 1 and m is 0.
- the compound of Formula XI can be defined by Formula XIb:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 3 and R 3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted hetero
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XI, Formula XIa, and Formula XIb, R 1 and R 1’ are the same. In some examples of Formula XI, Formula XIa, and Formula XIb, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XI, Formula XIa, and Formula XIb, R 1 and R 1’ are both hydrogen. In some examples of Formula XI, Formula XIa, and Formula XIb, R 1 and R 1’ are both–CH 3 .
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are substituted or unsubstituted alkylaryl.
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are substituted or unsubstituted aryl.
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are chosen from the m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are substituted or unsubstituted phenyl.
- Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are the same. In some examples of Formula XI, Formula XIa, and Formula XIb, R 3 and R 3’ are hydrogen.
- Formula XI, Formula XIa, and Formula XIb, R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
- Formula XI, Formula XIa, and Formula XIb, R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula XI, Formula XIa, and Formula XIb, R 8 and R 9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XI, Formula XIa, and Formula XIb, R 8 and R 9 are substituted or unsubstituted aryl.
- R 8 and R 9 are independently cho n fr m h m i i h n l
- the compound can be defined by Formula XII:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 5 and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XII, m is 0. In some examples of Formula XII, n is 1. In some examples of Formula XII, m is 1. In some examples of Formula XII, at least one of n and m is 1. In some examples of Formula XII, n and m are both 1.
- n and m are both 0.
- the compound of Formula XII can be defined by Formula XIIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 5 and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n 1 and m is 0.
- the compound of Formula XII can be defined by Formula XIIb:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 5 and R 5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl,
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are the same. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are both hydrogen. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are both–CH3.
- Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are substituted or unsubstituted alkylaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are substituted or
- Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are chosen from the moieties shown below ; wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
- EDG represents an electron donating group
- EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are substituted or unsubstituted phenyl.
- Formula XII Formula XIIa, and Formula XIIb, R 5 and R 5’ are the same. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 5 and R 5’ are hydrogen.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are substituted or unsubstituted alkylaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are substituted or unsubstituted aryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are independently cho n fr m h m i i h n l
- the compound can be defined by Formula XIII:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 and R 2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XIII, m is 0. In some examples of Formula XIII, n is 1. In some examples of Formula XIII, m is 1. In some examples of Formula XIII, at least one of n and m is 1. In some examples of Formula XIII, n and m are both 1.
- n and m are 0.
- the compound of Formula XIII can be defined by Formula XIIIa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 and R 2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or un
- n 1 and m is 0.
- the compound of Formula XIII can be defined by Formula XIIIb:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 2 and R 2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are the same. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are both hydrogen. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 1 and R 1’ are both–CH 3 .
- Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are substituted or unsubstituted alkylaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are substituted or
- Formula XII In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are substituted or unsubstituted phenyl.
- Formula XII In some examples of Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are the same. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R 2 and R 2’ are hydrogen.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are substituted or unsubstituted alkylaryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are substituted or unsubstituted aryl.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are independently cho n fr m h m i i h n l
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- Formula XII, Formula XIIa, and Formula XIIb, R 8 and R 9 are substituted or unsubstituted phenyl.
- the compound can be defined by Formula XIV:
- n 0 or 1;
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 and R 1’ are the same. In some examples of Formula XIV, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XIV, R 1 and R 1’ are both hydrogen. In some examples of Formula XIV, R 1 and R 1’ are both– CH 3 .
- R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are substituted or unsubstituted alkylaryl.
- R 8 and R 9 are substituted or unsubstituted aryl.
- R 8 and R 9 are independently chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 and R 9 are substituted or unsubstituted phenyl.
- n is 0. In some examples of Formula XIV, m is 0. In some examples of Formula XIV, n is 1. In some examples of Formula XIV, m is 1. In some examples of Formula XIV, at least one of n and m is 1. In some examples of Formula XIV, n and m are both 1.
- n and m are both 0.
- the compound of Formula XIV can be defined by Formula XIVa:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 and R 1’ are the same. In some examples of Formula XIVa, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XIVa, R 1 and R 1’ are both hydrogen. In some examples of Formula XIVa, R 1 and R 1’ are both– CH 3 .
- R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are substituted or unsubstituted alkylaryl.
- R 8 and R 9 are substituted or unsubstituted aryl.
- R 8 and R 9 are independently chosen from the moieties shown be
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- R 9 is substituted or unsubstituted phenyl.
- R 1 and R 1’ are both hydrogen.
- the compound of Formula XIVa can be defined by Formula XIVb:
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 8 and R 9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are substituted or unsubstituted alkylaryl.
- R 8 and R 9 are substituted or unsubstituted aryl.
- R 8 and R 9 are independently chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- R 9 is substituted or unsubstituted phenyl.
- R 9 is phenyl.
- the compound of Formula XIVa can be defined by Formula XIVc:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 and R 1’ are the same. In some examples of Formula XIVc, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XIVc, R 1 and R 1’ are both hydrogen. In some examples of Formula XIVc, R 1 and R 1’ are both– CH 3 .
- R 8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVc, R 8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVc, R 8 is substituted or unsubstituted aryl.
- R 8 is independently chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- R 1 and R 1’ are both hydrogen and R 9 is phenyl.
- the compound of Formula XIVa can be defined by Formula XIVd:
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVd, R 8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVd, R 8 is substituted or unsubstituted aryl.
- R 8 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- R 8 is phenyl, and the compound can be defined by the formula below.
- n 1 and m is 0.
- the compound of Formula XIV can be defined by Formula XIVe: R 9
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
- R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 and R 1’ are the same. In some examples of Formula XIVe, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XIVe, R 1 and R 1’ are both hydrogen. In some examples of Formula XIVe, R 1 and R 1’ are both– CH 3 .
- R 8 and R 9 are independently chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 8 and R 9 are independently chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are independently substituted or unsubstituted alkylaryl.
- R 8 and R 9 are independently substituted or unsubstituted aryl.
- R 8 and R 9 are independently is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- R 9 is substituted or unsubstituted phenyl.
- R 1 and R 1’ are both hydrogen.
- the compound of Formula XIVe can be defined by Formula XIVf:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R 9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or un
- R 8 and R 9 are independently chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- R 8 and R 9 are independently chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 and R 9 are independently substituted or unsubstituted alkylaryl.
- R 8 and R 9 are independently substituted or unsubstituted aryl.
- R 8 and R 9 are independently chosen from the moieties shown bel
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- R 9 is substituted or unsubstituted phenyl.
- R 9 is phenyl.
- the compound of Formula XIVe can be defined by Formula XIVg:
- R 1 and R 1’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 1 and R 1’ are the same. In some examples of Formula XIVg, R 1 and R 1’ are both hydrogen or–CH 3 . In some examples of Formula XIVg, R 1 and R 1’ are both hydrogen. In some examples of Formula XIVg, R 1 and R 1’ are both–CH 3 .
- R 8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVg, R 8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVg, R 8 is substituted or unsubstituted aryl.
- R 8 is chosen from the moieties shown below ; wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIVg, R 8 is substituted or unsubstituted phenyl.
- R 1 and R 1’ are both hydrogen and R 9 is phenyl.
- the compound of Formula XIVe can be defined by Formula XIVh:
- R 8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVh, R 8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVh, R 8 is substituted or unsubstituted aryl.
- R 8 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 8 is
- EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
- R 8 is
- EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halogen) 3 ), and p is chosen from 1, 2, 3, 4 and 5.
- R 8 is substituted or unsubstituted phenyl.
- the compound can be selected from one of the formulas below: ,
- n 0 or 1;
- R 10 and R 10’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 12’ , R 13’ , R 14’ , R 15’ , R 16’ , and R 17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsub
- R 18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XV, n is 1. In some examples of Formula XV, R 10 and R 10’ are the same. In some examples of Formula XV, R 10 and R 10’ are both hydrogen or–CH 3 . In some examples of Formula XV, R 10 and R 10’ are both hydrogen. In some examples of Formula XV, R 10 and R 10’ are both– CH 3 .
- R 11 is selected from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 11 is hydrogen.
- R 12 and R 12’ are independently chosen from hydrogen, hydroxy, and halogen.
- R 12 is hydrogen.
- R 12’ is hydrogen.
- R 12 and R 12’ are the same.
- R 12 and R 12’ are both hydrogen.
- R 13 and R 13’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 13 is hydrogen. In some examples of Formula XV, R 13’ is hydrogen. In some examples of Formula XV, R 13 and R 13’ are the same. In some examples of Formula XV, R 13 and R 13’ are both hydrogen.
- R 12 , R 12’ , R 13 and R 13’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 12 , R 12’ , R 13 and R 13’ are the same. In some examples of Formula XV, R 12 , R 12’ , R 13 and R 13’ are all hydrogen.
- R 12 and R 13 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XV, R 12 and R 13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
- R 12 and R 13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XV, R 12 and R 13 together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XV, R 12 and R 13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
- R 12’ and R 13’ together with the atoms to which they are attached form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms.
- R 12’ and R 13’ together with the atoms to which they are attached form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
- R 14 and R 14’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 14 is hydrogen. In some examples of Formula XV, R 14’ is hydrogen. In some examples of Formula XV, R 14 and R 14’ are the same. In some examples of Formula XV, R 14 and R 14’ are both hydrogen.
- R 15 and R 15’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 15 is hydrogen. In some examples of Formula XV, R 15’ is hydrogen. In some examples of Formula XV, R 15 and R 15’ are the same. In some examples of Formula XV, R 15 and R 15’ are both hydrogen.
- R 16 and R 16’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 16 is hydrogen. In some examples of Formula XV, R 16’ is hydrogen. In some examples of Formula XV, R 16 and R 16’ are the same. In some examples of Formula XV, R 16 and R 16’ are both hydrogen.
- R 14 , R 14’ , R 15 , and R 15’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 14 , R 14’ , R 15 , and R 15’ are the same. In some examples of Formula XV, R 14 , R 14’ , R 15 , and R 15’ are all hydrogen.
- R 14 , R 14’ , R 16 , and R 16’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 14 , R 14’ , R 16 , and R 16’ are the same. In some examples of Formula XV, R 14 , R 14’ , R 16 , and R 16’ are all hydrogen.
- R 15 , R 15’ , R 16 , and R 16’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R 15 , R 15’ , R 16 , and R 16’ are the same. In some examples of Formula XV, R 15 , R 15’ , R 16 , and R 16’ are all hydrogen.
- R 14 , R 14’ , R 15 , R 15’ , R 16 , and R 16’ are examples of Formula XV.
- R 14 , R 14’ , R 15 , R 15’ , R 16 , and R 16’ are the same.
- R 14 , R 14’ , R 15 , R 15’ , R 16 , and R 16’ are all hydrogen.
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 17 and R 17’ are independently substituted or unsubstituted alkylaryl.
- R 17 and R 17’ are independently substituted or unsubstituted aryl.
- R 17 and R 17’ are independently chosen from the moieties shown bel
- R 17 and R 17’ are independently substituted or unsubstituted phenyl.
- R 18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XV, R 18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XV, R 18 is substituted or unsubstituted aryl.
- R 18 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 18 is substituted or unsubstituted phenyl.
- the compound in some examples of Formula XV, can be defined by Formula XVa:
- n 0 or 1;
- R 10 and R 10’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 12 , R 13 , R 17 , R 12’ , R 13’ , and R 17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or
- unsubstituted thioalkyl substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
- R 18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XVa, n is 1.
- R 10 and R 10’ are the same. In some examples of Formula XVa, R 10 and R 10’ are both hydrogen or–CH 3 . In some examples of Formula XVa, R 10 and R 10’ are both hydrogen. In some examples of Formula XVa, R 10 and R 10’ are both– CH 3 .
- R 12 and R 12’ are independently chosen from hydrogen, hydroxy, and halogen.
- R 12 is hydrogen.
- R 12’ is hydrogen.
- R 12 and R 12’ are the same.
- R 12 and R 12’ are both hydrogen.
- R 13 and R 13’ are independently chosen from hydrogen, hydroxy, and halogen.
- R 13 is hydrogen.
- R 13’ is hydrogen.
- R 13 and R 13’ are the same.
- R 13 and R 13’ are both hydrogen.
- R 12 , R 12’ , R 13 and R 13’ are independently chosen from hydrogen, hydroxy, and halogen.
- R 12 , R 12’ , R 13 and R 13’ are the same.
- R 12 , R 12’ , R 13 and R 13’ are all hydrogen.
- R 12 and R 13 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XVa, R 12 and R 13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
- R 12 and R 13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVa, R 12 and R 13 together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVa, R 12 and R 13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
- R 12’ and R 13’ together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XVa, R 12’ and R 13’ together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 17 and R 17’ are independently substituted or unsubstituted alkylaryl.
- R 17 and R 17’ are independently substituted or unsubstituted aryl.
- R 17 and R 17’ are independently chosen from the moieties shown below
- R 17 and R 17’ are independently substituted or unsubstituted phenyl.
- R 18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVa, R 18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVa, R 18 is substituted or unsubstituted aryl.
- R 18 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 18 is substituted or unsubstituted phenyl.
- the compound in some examples of Formula XVa, can be defined by Formula XVb: R 17' R 17
- n 0 or 1;
- R 10 and R 10’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 17 and R 17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XVb, n is 1.
- R 10 and R 10’ are the same. In some examples of Formula XVb, R 10 and R 10’ are both hydrogen or–CH 3 . In some examples of Formula XVb, R 10 and R 10’ are both hydrogen. In some examples of Formula XVb, R 10 and R 10’ are both–CH 3 .
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVb, R 17 and R 17’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XVb, R 17 and R 17’ are independently substituted or unsubstituted aryl.
- R 17 and R 17’ are independently chosen from the moieties shown bel
- R 17 and R 17’ are independently substituted or unsubstituted phenyl.
- R 18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVb, R 18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVb, R 18 is substituted or unsubstituted aryl.
- R 18 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 18 is substituted or unsubstituted phenyl.
- the compound in some examples of Formula XVb, can be defined by the formula:
- the compound in some examples of Formula XVa, can be defined by Formula XVc: R 17 R 17
- n 0 or 1;
- R 10 and R 10’ are each independently chosen from H and substituted or unsubstituted C 1 -C 4 alkyl;
- R 12 , R 13 , R 17 , and R 17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R 12 and R 13 , together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and R 18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl,
- n is 0. In some examples of Formula XVc, n is 1.
- R 10 and R 10’ are the same. In some examples of Formula XVc, R 10 and R 10’ are both hydrogen or–CH 3 . In some examples of Formula XVc, R 10 and R 10’ are both hydrogen. In some examples of Formula XVc, R 10 and R 10’ are both– CH 3 .
- R 12 is chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVc, R 12 is hydrogen.
- R 13 is chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVc, R 13 is hydrogen.
- R 12 and R 13 are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVc, R 12 and R 13 are the same. In some examples of Formula XVc, R 12 and R 13 are both hydrogen.
- R 12 and R 13 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XVc, R 12 and R 13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
- R 12 and R 13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVc, R 12 and R 13 together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVc, R 12 and R 13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 17 and R 17’ are independently substituted or unsubstituted alkylaryl.
- R 17 and R 17’ are independently substituted or unsubstituted aryl.
- R 17 and R 17’ are independently chosen from the moieties shown bel
- R 17 and R 17’ are independently substituted or unsubstituted phenyl.
- R 18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVc, R 18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVc, R 18 is substituted or unsubstituted aryl.
- R 18 is chosen from the moieties shown below
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 18 is substituted or unsubstituted phenyl.
- the compound in some examples of Formula XVc, can be defined by Formula XVd:
- n 0 or 1;
- R 10 and R 10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl
- R 17 and R 17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
- alkylheterocycloalkyl substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
- R 18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- n is 0. In some examples of Formula XVd, n is 1.
- R 10 and R 10’ are the same. In some examples of Formula XVd, R 10 and R 10’ are both hydrogen or–CH 3 . In some examples of Formula XVd, R 10 and R 10’ are both hydrogen. In some examples of Formula XVd, R 10 and R 10’ are both–CH 3 .
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
- R 17 and R 17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 17 and R 17’ are independently substituted or unsubstituted alkylaryl.
- R 17 and R 17’ are independently substituted or unsubstituted aryl.
- R 17 and R 17’ are independently chosen from the moieties shown bel
- R 17 and R 17’ are independently substituted or unsubstituted phenyl.
- R 18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
- R 18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVd, R 18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVd, R 18 is substituted or unsubstituted aryl.
- R 18 is chosen from the moieties shown below ;
- EDG represents an electron donating group and EWG represents an electron withdrawing group
- p is chosen from 1, 2, 3, 4 and 5.
- R 18 is substituted or unsubstituted phenyl.
- silane compounds described herein can be prepared using synthetic
- silane compounds can be prepared from readily available starting materials. Optimum reaction conditions can vary with the particular reactants or solvents used, but such conditions can be determined by one skilled in the art.
- Variations on the compounds discussed herein include the addition, subtraction, or movement of the various constituents as described for each compound. Similarly, when one or more chiral centers are present in a molecule, the chirality of the molecule can be changed. Additionally, compound synthesis can involve the protection and deprotection of various chemical groups. The use of protection and deprotection, and the selection of appropriate protecting groups can be determined by one skilled in the art. The chemistry of protecting groups can be found, for example, in Wuts and Greene, Protective Groups in Organic Synthesis, 4th Ed., Wiley & Sons, 2006, which is incorporated herein by reference in its entirety.
- the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, WI), Acros Organics (Morris Plains, NJ), Fisher Scientific (Pittsburgh, PA), Sigma (St.
- Reactions to produce the compounds described herein can be carried out in solvents, which can be selected by one of skill in the art of organic synthesis.
- Solvents can be substantially nonreactive with the starting materials (reactants), the intermediates, or products under the conditions at which the reactions are carried out (e.g., temperature and pressure).
- Reactions can be carried out in one solvent or a mixture of more than one solvent.
- Product or intermediate formation can be monitored according to any suitable method known in the art.
- product formation can be monitored by
- spectroscopic means such as nuclear magnetic resonance spectroscopy (e.g., 1 H NMR and/or 13 C NMR), infrared spectroscopy (e.g., FT-IR spectroscopy), spectrophotometry (e.g., UV-visible spectrometry), mass spectrometry, and/or by chromatography such as high performance liquid chromatography (HPLC) or thin layer chromatography.
- nuclear magnetic resonance spectroscopy e.g., 1 H NMR and/or 13 C NMR
- infrared spectroscopy e.g., FT-IR spectroscopy
- spectrophotometry e.g., UV-visible spectrometry
- mass spectrometry e.g., mass spectrometry
- chromatography such as high performance liquid chromatography (HPLC) or thin layer chromatography.
- silane compounds can be prepared from 1,1 '-Bi-2-naphthol (BINOL) or derivatives thereof, as generally illustrated in Scheme 1.
- BINOL 1,1 '-Bi-2-naphthol
- Scheme 1 BINOL-Based S nthesis of Silane Com ounds.
- halogenation using methods known in the art (see, for example, Takaya H et al., Org. Syn. 1989, 67, 20–32) can afford compound 1.1 (dibromobinaphthalene).
- Compound 1.1 can then be converted to compound 1.2 by treatment with lithium tetramethylpiperidide (LiTMP) and trimethylsilyl chloride (TMSCl), followed by reaction with ICl to form an aryl iodide intermediate, followed by palladium- catalyzed cross-coupling of the aryl iodide intermediate with phenyl boronic acid.
- LiTMP lithium tetramethylpiperidide
- TMSCl trimethylsilyl chloride
- silacyclization of 1.2 can be accomplished, for example, by lithium halogen exchange (e.g., effected with n-BuLi) followed by treatment with silicon tetrachloride to generate a dichlorosilane mtermediate in situ.
- the dichlorosilane intermediate can then be hydrolvzed (e.g., by subjection to ether and water) to afford compound 1.3.
- Silane compounds containing a variety of substituents at various positions on the binaphthyl back bone can be prepared using modified versions of the methodologies outlined above.
- silane compounds including substituents at both the 4, 4’ and 6, 6’ positions can be prepared using the methods outlined in Scheme 4. Drawing from established protocols (see, for example, Hu QS et al., J. Org. Chem. 1999, 64, 7528–7536), (R)-BINOL can be bis-O-hexylated, followed by four-fold bromination and dealkylation with BBr 3 to afford compound 4.1.
- silane compound 4.2 Suzuki-Miyaura cross-coupling with PhB(OH) 2 , subsequent triflation of the free alcohols, and Nickel-catalyzed Kumada cross-coupling with MeMgBr can provides compound 4.2.
- Silacyclization can then be performed as described above to prepare the silane compounds. Briefly, deprotonation of both benzylic methyl groups with n-BuLi/TMEDA, followed by quenching with Si(OMe) 4 , can afford silane compound 4.1. Subsequent hydrolysis with dilute HCl can afford silane compound 4.2
- 6,6'-diphenyl substituted silane compounds can be prepared using a procedure similar to the procedure outlined for preparation of the 4, 4', 6, 6' tetrasubstituted compounds.
- An example methodology is outlined in Scheme 5. The methodology can involve a regi.o-control.led dibromination of a bis-ethylated ( ?)-BINOL intermediate at the 6 and 6' positions, followed by a Suzuki-Miyaura cross-coupling proceeding dealkylation to affix substituents at the 6 and 6' positions.
- 4,4'-diphenyl substituted silane compounds can be prepared using the synthetic methodology outlined in Scheme 6.
- 2- (trimethylsilyl)phenyltriflate can be reacted with benzoylacetone in the presence of CsF to afford 4-phenyl-2-naphthol (compound 6.1).
- Oxidative coupling with CuTMEDA, followed by resolution with S-(+)-camphorsulfonyl chloride can provide, after removal of the chiral auxiliary, enantiopure 6.2.
- silane compounds described herein can be used as enantioselective
- organocatalysts comprising a silane compound described herein.
- the silane compounds described herein can be used to catalyze a nucleophilic conjugate addition reaction, in which a first organic species comprising a nitroalkene reacts with a second organic species comprising a nucleophile to provide a product.
- the silane compounds described herein can also be used to catalyze an acyl-Mannich type reaction in which a first organic species comprising an amine reacts with a second organic species comprising a carbonyl containing compound to provide a product.
- the silane compounds described herein can also be used to catalyze an epoxide ring opening reaction, in which a first organic species comprising an epoxide reacts with a second organic species comprising a nucelophile to provide a product.
- the silane compounds described herein can be used to catalyze the sequestration of carbon dioxide, in which a first organic species comprising carbon dioxide reacts with a second organic species comprising a reservoir to provide a product.
- the silane compounds described herein can be used to catalyze an enantioselective reaction. In these cases, the first organic species reacts with the second organic species to form a chiral product.
- the product can preferably be enantioentriched.
- Methods of using the silane compounds described herein as catalysts can involve contacting the first organic species and the second organic species with a catalytically effective amount of a silane compound or a catalyst composition comprising a silane compound under conditions effective to form the product.
- silane compounds described herein can also be used as sensors for analytes.
- suitable analytes include, for example, anions and chiral compounds.
- the methods comprise contacting the sample comprising an analyte with a silane compound described herein; and evaluating an optical property of the silane compound to detect, identify, or quantify the analyte.
- the silane compounds can exhibit a spectroscopically observable change (e.g., a colorimetric and/or fluorometric response) in the presence of the analyte of interest.
- the silane compound can be a luminophore.
- the spectroscopically observable change can be a change in the absorbance of the silane compound (i.e., color), a change in the fluorescence of the silane compound, a change in the phosphorescence of the silane compound, or a combination thereof.
- methods for detecting, identifying, and/or quantifying an analyte in a sample can comprise (a) contacting the sample comprising an analyte with a silane compound described herein; and (b) evaluating the optical properties of the silane compound to elucidate the presence of an analyte, to identity an analyte, to determine the concentration of an analyte, or combinations thereof.
- the methods can comprise evaluating the optical properties of the silane compound to determine the concentration of an analyte.
- one or more spectroscopically observable changes in a silane compound are qualitatively observed to detect the presence of an analyte in a sample.
- the absorbance of the silane compound i.e., color
- the fluorescence of the silane compound under irradiation by, for example a UV blacklight
- one or more spectroscopically observable changes in a silane compound are measured as part of an assay to quantify the amount of analyte in a sample.
- the silane compounds can be used in a fluorescence-based assay for the detection and/or quantification of an analyte.
- Fluorescence assays involve the observation and/or measurement of changes in the fluorescence of a silane compound upon contact with an analyte.
- the change may take one or more of several forms, including a change in emission spectra, a change in the intensity of the fluorescence (i.e., fluorescence quantum yield), and a change in the fluorescence lifetime. These changes may be either in the positive or negative direction and may be of a range of magnitudes, which preferably will be detectable as described below.
- the emission spectra of a fluorophore sensor can be measured using a
- the spectrofluorometer uses a high intensity light source with a particular wavelength (or interval of wavelengths) to excite the fluorophore. The spectrofluorometer then measures the intensity of light emitted by the fluorophore at a range of different wavelengths, called an emission spectra. Changes in the maximum emission wavelength or the shape of the emission spectra that are caused by an analyte of interest in a sample may be used to determine the presence or concentration of the analyte of interest in the sample.
- the silane compound can be designed to exhibit a large change in maximum emission wavelength upon exposure to the analyte of interest.
- the maximum emission wavelength of the silane compound shifts by more than 50 nm, more preferably by more than 75 nm, most preferably by more than 100 nm upon exposure to the analyte of interest.
- Changes in the maximum emission wavelength can also be observed with the naked eye, for example with the use of a handheld blacklight, to qualitatively determine the presence of the analyte of interest in a sample.
- the fluorescence quantum yield of a silane compound can be measured using methods known in the art. See, for example, Lakowicz, J. R.“Principles of Fluorescence Spectroscopy”, 2 nd Ed., Plenum Press, New York, 1999. Generally, the fluorescence quantum yield of the silane compound is obtained by comparison of the integrated area of the corrected emission spectrum of the sensor with that of a reference solution.
- a change in the fluorescence quantum yield of the silane compound upon exposure to an analyte of interest may be used as the basis for detecting the presence of the analyte of interest in a sample, and may optionally be used to determine the concentration of the analyte of interest in a sample.
- the silane compound will preferably be selected so as to exhibit a large change in fluorescence quantum yield upon exposure to the analyte of interest.
- exposure of the silane compound to the analyte of interest results in at least a 10% reduction in the fluorescence quantum yield of the silane compound (e.g., at least a 25% reduction in the fluorescence quantum yield of the silane compound, at least a 50% reduction in the fluorescence quantum yield of the silane compound, at least a 75% reduction in the fluorescence quantum yield of the silane compound, or at least a 90% reduction in the fluorescence quantum yield of the silane compound).
- exposure of the silane compound to the analyte of interest can result in at least a 25% increase in the fluorescence quantum yield of the silane compound (e.g., at least a 50% increase in the fluorescence quantum yield of the silane compound, at least a 75% increase in the fluorescence quantum yield of the silane compound, at least a 100% increase in the fluorescence quantum yield of the silane compound, at least a 500% increase in the fluorescence quantum yield of the silane compound, or at least a 1000% increase in the fluorescence quantum yield of the silane compound).
- at least a 25% increase in the fluorescence quantum yield of the silane compound e.g., at least a 50% increase in the fluorescence quantum yield of the silane compound, at least a 75% increase in the fluorescence quantum yield of the silane compound, at least a 100% increase in the fluorescence quantum yield of the silane compound, at least a 500% increase in the fluorescence quantum yield of the silane compound, or at least a 1000% increase in
- the fluorescence lifetime of a silane compound can also be measured using methods known in the art. Changes in the fluorescence lifetime of a silane compound upon exposure to an analyte can also be used to determine the presence or concentration of an analyte in the sample.
- Hydrogen bond donor (HBD) catalysis is evolving as a powerful direction in organic catalysis.
- Two avenues through which HBD organocatalysts are proposed to operate include the more traditional hydrogen-bonding activation of appropriate functional groups found on electrophiles, and the more recently introduced ion-pairing catalysis.
- halide-binding is discussed as a promising new direction for enantioselective silanediol catalysis.
- (R)-2,2’-Dimethyl-1,1’-binaphthyl (11) A 250 mL 2-necked round bottom flask was equipped with a stir bar, flame dried, placed under N 2 atmosphere, and charged with (R)-Trifluoromethanesulfonic acid 2’-trifluoromethanesulfonyloxy [1,1’]binapthalenyl-2-yl ester (12.83 g, 23.3 mmol). Dry Et2O (160 mL) was added, followed by Ni(dppp)Cl2 (631 mg, 1.16 mmol, 0.05 equiv.).
- TMEDA N,N,N’,N’- tetramethylethylenediamine
- the solution was concentrated, diluted in 5 mL CH 2 Cl 2 , and quickly run through a short silica gel plug packed with hexanes using 1500 mL of 80/20 hexanes/EtOAc as the eluent.
- the eluent was concentrated to afford a yellow oil which was placed under an Ar atmosphere.
- the crude mixture stood undisturbed under Ar for 24 h, during which time clear, colorless crystals formed. After 24 h, the crystals were carefully triturated with 3 x 3 mL portions of hexanes to afford 396 mg of the desired silacycle (1.07 mmol, 31%).
- Tetrabutylammonium Chloride A solution of R-3 (5.0 x 10-3 M) in CDCl 3 was prepared in a 2 mL volumetric flask. Portions of TBACl were quantitatively transferred to the flask and 1 H NMR spectra of the solutions were recorded after the addition of each equivalent, ensuring that the concentration of R-3 did not change.
Abstract
Provided herein are silane compounds. The silane compounds can be used as organocatalysts and as sensors. Accordingly, also provided are methods of using the silane compounds described herein as catalysts. Methods of using the silane compounds described herein as catalysts can involve contacting a first organic species and a second organic species with a catalytically effective amount of a silane compound or a catalyst composition comprising a silane compound under conditions effective to form the desired product. The product can preferably be enantioenriched.
Description
SILANE COMPOUNDS AND METHODS OF USING THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 61/978,402 filed April 11, 2014, which is hereby incorporated herein by reference in its entirety.
BACKGROUND
Many complex organic compounds, including many clinically approved
pharmaceuticals, contain one or more chiral centers and may be provided in the form of one or more stereoisomers. In such cases, the multistep synthesis of complex organic compounds can employ stereoselective synthetic steps to provide, for example, enantioenriched compositions of a desired stereoisomer. For example, the synthesis of bioactive compounds such as Vinblastine, Lexapro, and Cialis can involve the stereoselective syntheses of arene rich triaryl- or diaryl- functionalities.
A variety of stereoselective synthetic methodologies are known in the art, including stereoselective methods for the preparation of triaryl- and diaryl- methanes. However, many existing methods for preparing compounds in a stereoselective manner are inefficient (e.g., low yielding) and/or require the use of enantioenriched substrates. Improved stereoselective synthetic methodologies for preparing a variety of complex organic compounds, including triaryl- and diaryl- methanes, are needed.
SUMMARY
Provided herein are compounds defined by Formula I:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R4, R5, and R6 (i.e., R2-R6) and R2’, R3’, R4’, R5’, and R6’ (i.e., R2’-R6’) are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, R3 and R4, R4 and R5, R5 and R6, R2’ and R3’, R3’ and R4’, R4’ and R5’, R5’ and R6’, , or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R7 and R7’ are each independently chosen from H, OH, and halogen; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
or wherein, as valence and stability permit, R8 and R9, together with the atoms to which they are attached, form a 7-9 membered silacycle;
with the proviso that when R8 and R9, together with the atoms to which they are attached, form a 7-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both phenyl.
In some examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R2-R7 and R2’-R7’ are not all H.
In some examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1 and R1’ are not both–CH3; and R2-R7 and R2’-R7’ are not all H.
In certain examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from the moieties shown below.
In some examples of Formula I, the compound can be defined by Formula II:
wherein n, m, R1, R1’, R2, R3, R4, R5, R6, R2’, R3’, R4’, R5’, R6’, R7, and R7’ are as defined above with respect to Formula I, with the proviso that when n=0 and m=0, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both phenyl.
In some examples of Formula II, the compound exhibits C2-symmetry.
In some examples of Formula II, when n=1 and m=1, R1, R1’, R2-R7 and R2’-R7’ are not all H.
In some examples of Formula II, when n=1 and m=1; R1 and R1’ are not both–CH3; and R2-R7 and R2’-R7’ are not all H.
In certain examples of Formula II, when n=1 and m=1, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from the moieties shown below.
wherein n, m, R1, R1’, R2, R3, R5, R2’, R3’, and R5’ are as defined above with respect to Formula I, with the proviso that when n=0 and m=0, R1, R1’, R3, R5, R3’ and R5’ are not all H and R2 and R2’ are not both phenyl.
In some examples of Formula III, n and m are both 1 and the compound can be defined by Formula IIIa:
wherein R1, R1’, R2, R3, R5, R2’, R3’, and R5’ are as defined above with respect to Formula I.
In some examples of Formula II, the compound can be defined by Formula IV:
wherein n, m, R1, R1’, R3, R5, R3’, and R5’ are as defined above with respect to Formula I.
In some examples of Formula IV, n and m are both 1 and the compound can be defined by Formula IVa:
wherein R1, R1’, R3, R5, R3’, and R5’ are as defined above with respect to Formula I.
In some examples of Formula II, the compound can be defined by Formula V:
wherein n, m, R1, R1’, R3, and R3’ are as defined above with respect to Formula I.
In some examples of Formula V, n and m are both 1 and the compound can be defined by Formula Va:
wherein R1, R1’, R3, and R3’ are as defined above with respect to Formula I.
In some examples of Formula II, the compound can be defined by Formula VI:
wherein n, m, R1, R1’, R5, and R5’ are as defined above with respect to Formula I.
In some examples of Formula VI, n and m are both 1 and the compound can be defined by Formula VIa:
wherein R1, R1’, R5, and R5’ are as defined above with respect to Formula I.
In some examples of Formula II, the compound can be defined by Formula VII:
wherein n, m, R1, R1’, R2, and R2’ are as defined above with respect to Formula I, with the proviso that when n=0 and m=0, R1 and R1’ are not both H and R2 and R2’ are not both phenyl.
In some examples of Formula VII, n and m are both 1 and the compound can be defined by Formula VIIa:
VIIa
wherein R1, R1’, R2, and R2’ are as defined above with respect to Formula I.
In some examples of Formula II, the compound can be defined by Formula VIII:
wherein n, m, R1, and R1’ are as defined above with respect to Formula I.
In some examples of Formula VIII, n and m are both 1 and the compound can be defined by Formula VIIIa:
wherein R1 and R1’ are as defined above with respect to Formula I.
In some examples, the compound can be one of the following:
wherein n, m, R1, R1’, R2, R3, R5, R2’, R3’, R5’, R8, and R9 are as defined above with respect to Formula I.
In some examples of Formula IX, m is 0. In some examples of Formula IX, R9 is substituted or unsubstituted aryl. In certain examples of Formula IX, m is 0 and R9 is substituted or unsubstituted aryl. For example, in certain examples of Formula IX, m is 0
and R9 is substituted or unsubstituted phenyl. In certain examples of Formula IX, R8 is chosen from the m i i h n l
In some examples of Formula I, the compound can be defined by Formula X:
wherein n, m, R1, R1’, R3, R5, R3’, R5’, R8, and R9 are as defined above with respect to Formula I.
In some examples of Formula X, m is 0. In some examples of Formula X, R9 is substituted or unsubstituted aryl. In certain examples of Formula X, m is 0 and R9 is substituted or unsubstituted aryl. For example, in certain examples of Formula X, m is 0 and R9 is substituted or unsubstituted phenyl. In certain examples of Formula X, R8 is chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula I, the compound can be defined by Formula XI:
XI
wherein n, m, R1, R1’, R3, R3’, R8, and R9 are as defined above with respect to Formula I.
In some examples of Formula XI, m is 0. In some examples of Formula XI, R9 is substituted or unsubstituted aryl. In certain examples of Formula XI, m is 0 and R9 is substituted or unsubstituted aryl. For example, in certain examples of Formula XI, m is 0 and R9 is substituted or unsubstituted phenyl. In certain examples of Formula XI, R8 is chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula I, the compound can be defined by Formula XII:
R5 R5'
wherein n, m, R1, R1’, R5, R5’, R8, and R9 are as defined above with respect to Formula I.
In some examples of Formula XII, m is 0. In some examples of Formula XII, R9 is substituted or unsubstituted aryl. In certain examples of Formula XII, m is 0 and R9 is substituted or unsubstituted aryl. For example, in certain examples of Formula XII, m is 0 and R9 is substituted or unsubstituted phenyl. In certain examples of Formula XII, R8 is chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula I, the compound can be defined by Formula XIII:
wherein n, m, R1, R1’, R2, R2’, R8, and R9 are as defined above with respect to Formula I.
In some examples of Formula XIII, m is 0. In some examples of Formula XIII, R9 is substituted or unsubstituted aryl. In certain examples of Formula XIII, m is 0 and R9 is substituted or unsubstituted aryl. For example, in certain examples of Formula XIII, m is 0 and R9 is substituted or unsubstituted phenyl. In certain examples of Formula XIII, R8 is chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula I, the compound can be defined by Formula XIV:
XIV
wherein n, m, R1, R1’, R8, and R9 are as defined above with respect to Formula I.
In some examples of Formula XIV, m is 0. In some examples of Formula XIV, R9 is substituted or unsubstituted aryl. In certain examples of Formula XIV, m is 0 and R9 is substituted or unsubstituted aryl. For example, in certain examples of Formula XIV, m is 0 and R9 is substituted or unsubstituted phenyl. In certain examples of Formula XIV, R8 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some exam les, the com ound can be one of the followin :
,
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R11, R12, R13, R14, R15, R16, R17, R12’, R13’, R14’, R15’, R16’, and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R11 and R12, R12 and R13, R13 and R14, R14 and R15, R15 and R16, R16 and R17, R12’ and R13’, R13’ and R14’, R14’ and R15’, R15’ and R16’, or R16’ and R17’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XV, the compound can be defined by Formula XVa:
wherein n, R10, R10’, R12, R13, R17, R12’, R13’, R17’, and R18 are as defined above with respect to Formula XV.
In some examples of Formula XVa, the compound can be defined by Formula XVb: R17' R17
wherein n, R10, R10’, R17, R17’, and R18 are as defined above with respect to Formula XV.
In some examples of Formula XVb, the compound can be defined by the formula:
In some examples of Formula XVa, the compound can be defined by Formula XVc: R17 R17
wherein n, R10, R10’, R12, R13, R17, R17’, and R18 are as defined above with respect to Formula XV.
In some examples of Formula XVc, the compound can be defined by Formula XVd:
wherein n, R10, R10’, R17, R17’, and R18 are as defined above with respect to Formula XV.
In certain examples, the compounds described above can be in a complex with a suitable solvent, such as diethyl ether. For example, in some cases, the compounds can be in a 2:1 complex with diethyl ether.
The silane compounds provided herein can be used as organocatalysts. For example, the silane compounds described herein can be used to catalyze a nucleophilic conjugate addition reaction in which a first organic species comprising a nitroalkene reacts with a second organic species comprising a nucleophile to provide a product. The silane compounds described herein can also be used to catalyze an acyl-Mannich type reaction in which a first organic species comprising an amine reacts with a second organic species comprising a carbonyl containing compound to provide a product.
Accordingly, also provided are methods of using the silane compounds described herein as catalysts. Methods of using the silane compounds described herein as catalysts can involve contacting a first organic species and a second organic species with a catalytically effective amount of a silane compound or a catalyst composition comprising a silane compound under conditions effective to form the desired product. The product can preferably be enantioenriched.
The silane compounds described herein can also be used as sensors for analytes. Examples of suitable analytes include, for example, anions and chiral compounds.
Accordingly, also provided are methods for detecting, identifying, and/or quantifying an analyte in a sample. The methods comprise contacting the sample comprising an analyte with a silane compound described herein; and evaluating an optical property of the silane compound to detect, identify, or quantify the analyte.
DESCRIPTION OF FIGURES
Figure 1 displays the chiral HPLC of 9a formed using 8-TMS and 20 mol% R-3. Figure 2 displays the chiral HPLC of 9a formed using 8-TBS and 20 mol% R-3. Figure 3 displays the chiral HPLC of 9a formed using 8-TIPS and 20 mol% R-3.
Figure 4 displays the chiral HPLC of 9a formed using 8-TIPS and 100 mol% R-3. Figure 5 displays the chiral HPLC of 2,2,2-trichloroethyl 5-bromo-1-(1-methoxy-2- methyl-1-oxopropan-2-yl)isoquinoline-2(1H)-carboxylate (9b) formed using 8-TIPS and 20 mol % R-3.
Figure 6 displays the chiral HPLC of 9b formed using 8-TBS, 20 mol% R-3.
Figure 7 displays the chiral HPLC of 2,2,2-trichloroethyl 5-chloro-1-(1-methoxy-2- methyl-1-oxopropan-2-yl)isoquinoline-2(1H)-carboxylate (9c) formed using 8-TIPS, 20 mol % R-3.
Figure 8 displays the chiral HPLC of 9c formed using 8-TBS and 20 mol% R-3. Figure 9 displays the chiral HPLC of 2,2,2-trichloroethyl 1-(1-methoxy-2-methyl-1 - oxopropan-2-yl)-5-nitroisoquinoline-2(1H)-carboxylate (9d) formed using 8-TIPS, 20 mol % R-3.
Figure 10 displays the chiral HPLC of 9d formed using 8-TBS, 20 mol% R-3.
Figure 11 displays the chiral HPLC of racemic mixture of 9a.
Figure 12 displays the chiral HPLC of racemic mixture of 9b.
Figure 13 displays the chiral HPLC of racemic mixture of 9c.
Figure 14 displays the chiral HPLC of racemic mixture of 9d.
Figure 15 displays the chiral HPLC of an enantiopure Bis(TMS) derivative of Silanediol R-3.
Figure 16 displays the chiral HPLC of racemic Bis(TMS) derivative of Silanediol R- 3.
Figure 17 displays the chiral HPLC of S2 formed using S1, 20 mol% R-3.
Figure 18 displays the chiral HPLC of racemic S2.
Figure 19 displays the ORTEP representation of bis-trimethylsilyl protected (R)-3. Figure 20 displays the 1H NMR spectra of (R)-3 with varying equivalents of tetrabutylammonium chloride (TBACl). The–OH chemical shifts are marked with a circle.
Figure 21 displays the ORTEP representation of an ion-pair between achiral silanediol 1 and the HCl salt of isoquinoline. In the solid state, the O1-Cl and N-Cl distances are 2.12 Å and 2.32 Å respectively, indicative of moderately strong hydrogen bonds (Steiner T, Angew. Chem. Int. Ed. 2002, 41, 48-76). The O2-Cl bond is longer, with a distance of 4.47 Å.
Figure 22 displays the crystal structure of H2O complex of (±)-21b.
Figure 23 displays the crystal structure of bis-TMS derivative of (R)-22.
Figure 24 displays the crystal structure of a trimer derived from (R)-22b. The anisotropic displacement parameters are drawn at the 50% probability level.
Figure 25 displays the pKas and anion binding constants for representative silanediols.
Figure 26 illustrates the 1H NMR binding titration of silanediol (R)-22b with n-
Figure 27 illustrates the Job’s plot analysis of (R)-22b and n-Bu4NCl in CDCl3. Figure 28 displays the crystal structure of ion pair between di(naphthalen-1- yl)silanediol and the HCl salt of isoquinoline.
Figure 29 displays the proposed reaction pathway for silanediol-catalyzed N-acyl Mannich reaction of isoquinolines.
DETAILED DESCRIPTION
The materials, compounds, compositions, articles, devices, and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples and Figures included therein.
Before the present materials, compounds, compositions, articles, devices, and methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.
Definitions
In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:
Throughout the description and claims of this specification the word“comprise” and other forms of the word, such as“comprising” and“comprises,” means including but not limited to, and is not intended to exclude, for example, other additives, components, integers, or steps.
As used in the description and the appended claims, the singular forms“a,”“an,” and“the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to“a composition” includes mixtures of two or more such compositions, reference to“an agent” includes mixtures of two or more such agents, reference to“the component” includes mixtures of two or more such components, and the like.
“Optional” or“optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
Ranges can be expressed herein as from“about” one particular value, and/or to “about” another particular value. By“about” is meant within 5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent“about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
It is understood that throughout this specification the identifiers“first” and“second” are used solely to aid in distinguishing the various components and steps of the disclosed subject matter. The identifiers“first” and“second” are not intended to imply any particular order, amount, preference, or importance to the components or steps modified by these terms.
As used herein, the term“substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, heteroatoms present in a compound or moiety, such as nitrogen, can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valency of the heteroatom. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms “substitution” or“substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously
undergo transformation such as by rearrangement, cyclization, elimination, etc.
“Z1,”“Z2,”“Z3,” and“Z4” are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.
The term“aliphatic” as used herein refers to a non-aromatic hydrocarbon group and includes branched and unbranched, alkyl, alkenyl, or alkynyl groups.
The term“alkyl” as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, for example 1 to 3, 1 to 4, 1 to 5, 1 to 6, 1 to 7, 1 to 8, 1 to 9, 1 to 10, or 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below.
Throughout the specification“alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. For example, the term“halogenated alkyl” specifically refers to an alkyl group that is substituted with one or more halides (halogens; e.g., fluorine, chlorine, bromine, or iodine). The term“alkoxyalkyl” specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term“alkylamino” specifically refers to an alkyl group that is substituted with one or more amino groups, as described below, and the like. When“alkyl” is used in one instance and a specific term such as“alkylalcohol” is used in another, it is not meant to imply that the term“alkyl” does not also refer to specific terms such as“alkylalcohol” and the like.
This practice is also used for other groups described herein. That is, while a term such as“cycloalkyl” refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can, in addition, be specifically identified herein; for example, a particular substituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specifically referred to as, e.g., a“halogenated alkoxy,” a particular substituted alkenyl can be, e.g., an“alkenylalcohol,” and the like. Again, the practice of using a general term, such as“cycloalkyl,” and a specific term, such as
“alkylcycloalkyl,” is not meant to imply that the general term does not also include the specific term.
The term“alkoxy” as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an“alkoxy” group can be defined as—OZ1 where Z1 is alkyl as defined above.
The term“alkenyl” as used herein is a hydrocarbon group of from 2 to 24 carbon atoms, for example, 2 to 5, 2 to 10, 2 to 15, or 2 to 20 carbon atoms, with a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (Z1Z2)C=C(Z3Z4) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below.
The term“alkynyl” as used herein is a hydrocarbon group of 2 to 24 carbon atoms, for example 2 to 5, 2 to 10, 2 to 15, or 2 to 20 carbon atoms, with a structural formula containing at least one carbon-carbon triple bond. The alkynyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below.
The term“aryl” as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl,
phenoxybenzene, and the like. The term“heteroaryl” is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The term“non-heteroaryl,” which is included in the term“aryl,” defines a group that contains an aromatic group that does not contain a heteroatom. The aryl or heteroaryl group can be substituted or unsubstituted. The aryl or heteroaryl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein. The term“biaryl” is a specific type of aryl group and is included in the definition of aryl. Biaryl refers to two aryl groups that are bound together via a fused ring
structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.
The term“cycloalkyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term“heterocycloalkyl” is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted. The cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
The term“cycloalkenyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms and containing at least one double bound, i.e., C=C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. The term“heterocycloalkenyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term“cycloalkenyl,” where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted. The cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
The term“cyclic group” is used herein to refer to either aryl groups, non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both. Cyclic groups have one or more ring systems that can be substituted or unsubstituted. A cyclic group can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups.
The term“carbonyl as used herein is represented by the formula–C(O)Z1 where Z1 can be a hydrogen, hydroxyl, alkoxy, alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. Throughout this specification“C(O)” or“CO” is a short hand notation for C=O.
The term“aldehyde” as used herein is represented by the formula—C(O)H.
The terms“amine” or“amino” as used herein are represented by the formula— NZ1Z2, where Z1 and Z2 can each be substitution group as described herein, such as hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.“Amido” is —C(O)NZ1Z2.
The term“carboxylic acid” as used herein is represented by the formula—C(O)OH. A“carboxylate” or“carboxyl” group as used herein is represented by the formula
- —C(O)O .
The term“ester” as used herein is represented by the formula—OC(O)Z1 or —C(O)OZ1, where Z1 can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
The term“ether” as used herein is represented by the formula Z1OZ2, where Z1 and Z2 can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
The term“ketone” as used herein is represented by the formula Z1C(O)Z2, where Z1 and Z2 can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
The term“halide” or“halogen” as used herein refers to the fluorine, chlorine, bromine, and iodine.
The term“hydroxyl” as used herein is represented by the formula—OH.
The term“nitro” as used herein is represented by the formula—NO2.
The term“silyl” as used herein is represented by the formula—SiZ1Z2Z3, where Z1, Z2, and Z3 can be, independently, hydrogen, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
The term“sulfonyl” is used herein to refer to the sulfo-oxo group represented by the formula—S(O)2Z1, where Z1 can be hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
The term“sulfonylamino” or“sulfonamide” as used herein is represented by the formula—S(O)2NH—.
The term“thiol” as used herein is represented by the formula—SH.
The term“thio” as used herein is represented by the formula—S—.
"R1," "R2," "R3," "Rn," etc, where n is some integer, as used herein can,
independently, possess one or more of the groups listed above. For example, if R1 is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an amine group, an alkyl group, a haiide, and the like. Depending upon the groups that are selected, a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase "an alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.
The term "electron donating group" (also abbreviated herein as EDG) is used herein to describe substituents (e.g., atoms or functional groups) that can donate some of their electron density into a conjugated π system to which they are attached (e.g., a benzene group) via resonance or inductive electron withdrawal, thus making the conjugated π system more nucieophilic. When attached to benzene, an electron donating group can, for example, make the benzene more likely to participate in electrophilic substitution reactions.
Examples of electron donating groups include, but are not limited to, primary, secondary and tertiary amines; hydroxy groups; amides; alkoxy groups; alkyl groups; and aryl groups.
The term "electron withdrawing group" (also abbreviated herein as EWG) is used herein to describe substituents (e.g., atoms or functional groups) that can remove electron density from a conjugated π system to which they are attached (e.g., benzene) via resonance or inductive electron withdrawal, thus making the π system more electrophilic. When attached to a benzene, and electron withdrawing group can, for example, make electrophilic aromatic substitution reactions slower and more complex. Depending on their relative strengths, electron withdrawing groups can also determine the positions (relative to themselves) on the benzene ring where substitutions can take place. Examples of electron withdrawing groups include, but are not limited to, nitro, quaternary amines, trihalides (e.g., -CFV), cyano, sulfonates, carboxylic acids, esters, aldehydes, and ketones.
Unless stated to the contrary, a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible stereoisomer or mixture of stereoisomer (e.g., each enantiomer, each diastereomer, each meso compound, a racemic mixture, or scalemic mixture).
Reference will now be made in detail to specific aspects of the disclosed materials,
compounds, compositions, articles, and methods, examples of which are illustrated in the accompanying Examples and Figures. Compounds
Provided herein are compounds defined by Formula I:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R4, R5, and R6 (i.e., R2-R6) and R2’, R3’, R4’, R5’, and R6’ (i.e., R2’-R6’) are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, R3 and R4, R4 and R5, R5 and R6, R2’ and R3’, R3’ and R4’, R4’ and R5’, R5’ and R6’, or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R7 and R7’ are each independently chosen from H, OH, and halogen; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or
unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
or wherein, as valence and stability permit, R8 and R9, together with the atoms to which they are attached, form a 7-9 membered silacycle;
with the proviso that when R8 and R9, together with the atoms to which they are attached, form a 7-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both phenyl.
In some examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R2-R7 and R2’-R7’ are not all H.
In some examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1 and R1’ are not both–CH3; and R2-R7 and R2’-R7’ are not all H.
In some examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl. In certain examples of Formula I, when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from the moieties shown below.
In some examples of Formula I, n is 0. In some examples of Formula I, m is 0. In some examples of Formula I, n and m are 0. In some examples of Formula I, n is 1. In some examples of Formula I, m is 1. In some examples of Formula I, at least one of n and m is 1. In some examples of Formula I, n and m are 1. In some examples of Formula I, n is 1 and m is 0.
In some examples of Formula I, R1 and R1’ are the same. In some examples of Formula I, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula I, R1 and R1’ are both hydrogen. In some examples of Formula I, R1 and R1’ are both–CH3.
In some examples of Formula I, R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula I, R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula I, R2 and R2’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula I, R2 and R2’ are independently substituted or unsubstituted aryl.
In some examples of Formula I, R2 and R2’ are independently chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula II, R2 and R2’ are independently substituted or unsubstituted phenyl.
In some examples of Formula I, R2 and R2’ are the same. In some examples of Formula I, R2 and R2’ are both hydrogen.
In some examples of Formula I, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula I, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula I, R3 and R3’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula I, R3 and R3’ are independently substituted or unsubstituted aryl.
In some examples of Formula I, R3 and R3’ are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula I, R3 and R3’ are independently substituted or unsubstituted phenyl.
In some examples of Formula I, R3 and R3’ are the same. In some examples of Formula I, R3 and R3’ are both hydrogen.
In some examples of Formula I, R4 and R4’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula I, R4 and R4’ are the same. In certain examples of Formula I, R4 and R4’ are both hydrogen.
In some examples of Formula I, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula I, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula I, R5 and R5’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula I, R5 and R5’ are independently substituted or unsubstituted aryl.
In some examples of Formula I, R5 and R5’ are independently chosen from the moieties shown below
In some examples of Formula I, R5 and R5’ are the same. In some examples of Formula I, R5 and R5’ are both hydrogen.
In some examples of Formula I, R3 and R3’ are the same, and R5 and R5’ are the same. In some examples of Formula I, R3, R3’, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula I, R3, R3’, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or
unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula I, R3, R3’, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula I, R3, R3’, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula I, R3, R3’, R5 and R5’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula I, R3, R3’, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula I, R3 and R3’ are both hydrogen, and R5 and R5’ are the same. In some examples of Formula I, R3 and R3’ are the same and R5 and R5’ are both hydrogen. In some examples of Formula I, R3, R3’, R5 and R5’ are all the same. In some examples of Formula I, R3, R3’, R5, and R5’ are all hydrogen.
In some examples of Formula I, R6 and R6’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula I, R6 and R6’ are the same. In certain examples of Formula I, R6 and R6’ are both hydrogen.
In some examples of Formula I, R7 and R7’ are the same. In some examples of Formula I, R7 and R7’ are both hydrogen.
In some examples of Formula I, R4, R6, R4’, and R6’ are the same. In some examples of Formula I, R4, R6, R4’, and R6’ are all hydrogen. In some examples of Formula I, R4, R7, R4’, and R7’ are the same. In some examples of Formula I, R4, R7, R4’, and R7’ are all hydrogen. In some examples of Formula I, R6, R7, R6’, and R7’ are the same. In some examples of Formula I, R6, R7, R6’, and R7’ are all hydrogen.
In some examples of Formula I, R4, R6, R7, R4’, R6’, and R7’ are the same. In some examples of Formula I, R4, R6, R7, R4’, R6’, and R7’ are all hydrogen.
In some examples of Formula I, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples
of Formula I, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula I, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula I, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula I, R8 and R9 are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula I, R8 and R9 are independently substituted or unsubstituted phenyl.
In some examples of Formula I, R8 and R9, together with the atoms to which they are attached, form a 7-9 membered silacycle, and the compound can be defined by Formula II:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R4, R5, and R6 (i.e., R2-R6) and R2’, R3’, R4’, R5’, and R6’ (i.e., R2’-R6’) are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl,
substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, R3 and R4, R4 and R5, R5 and R6, R2’ and R3’, R3’ and R4’, R4’ and R5’, or R5’ and R6’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R7 and R7’ are each independently chosen from H, OH, and halogen;
with the proviso that when n=0 and m=0, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both phenyl.
In some examples of Formula II, the compound exhibits C2-symmetry.
In some examples of Formula II, when n=1 and m=1, R1, R1’, R2-R7 and R2’-R7’ are not all H.
In some examples of Formula II, when n=1 and m=1; R1 and R1’ are not both–CH3; and R2-R7 and R2’-R7’ are not all H.
In some examples of Formula II, when n=1 and m=1, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula II, when n=1 and m=1, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl. In certain examples of Formula II, when n=1 and m=1 , R1, R1’, R3- R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from the moieties shown below.
In some examples of Formula II, n is 0. In some examples of Formula II, m is 0. In some examples of Formula II, n and m are 0. In some examples of Formula II, n is 1. In some examples of Formula II, m is 1. In some examples of Formula II, at least one of n and m is 1. In some examples of Formula II, n and m are 1.
In some examples of Formula II, R1 and R1’ are the same. In some examples of Formula II, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula II, R1 and R1’ are both hydrogen. In some examples of Formula II, R1 and R1’ are both–CH3.
In some examples of Formula II, R2 and R2’ are the same. In some examples of Formula II, R2 and R2’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula II, R2 and R2’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R2 and R2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R2 and R2’ are substituted or unsubstituted aryl.
In some examples of Formula II, R2 and R2’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula II, R2 and R2’ are substituted or unsubstituted phenyl.
In some examples of Formula II, R3 and R3’ are the same. In some examples of Formula II, R3 and R3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl,
substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula II, R3 and R3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula II, R3 and R3’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula II, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula II, R4 and R4’ are the same. In some examples of Formula II, R4 and R4’ are both chosen from hydrogen, hydroxy, and halogen. In certain examples of Formula II, R4 and R4’ are both hydrogen.
In some examples of Formula II, R5 and R5’ are the same. In some examples of Formula II, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula II, R5 and R5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula II, R5 and R5’ are chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula II, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula II, R3 and R3’ are the same, and R5 and R5’ are the same. In some examples of Formula II, R3, R3’, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula II, R3, R3’, R5 and R5’ are individually chosen from
substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula II, R3, R3’, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula II, R3, R3’, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula II, R3, R3’, R5 and R5’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula II, R3, R3’, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula II, R6 and R6’ are the same. In some examples of Formula II, R6 and R6’ are both chosen from hydrogen, hydroxy, and halogen. In certain examples of Formula II, R6 and R6’ are both hydrogen.
In some examples of Formula II, R7 and R7’ are the same. In some examples of Formula II, R7 and R7’ are both hydrogen.
In some examples of Formula II, R4, R6, R4’, and R6’ are the same. In some examples of Formula II, R4, R6, R4’, and R6’ are all hydrogen. In some examples of Formula II, R4, R7, R4’, and R7’ are the same. In some examples of Formula II, R4, R7, R4’, and R7’ are all hydrogen. In some examples of Formula II, R6, R7, R6’, and R7’ are the same. In some examples of Formula II, R6, R7, R6’, and R7’ are all hydrogen.
In some examples of Formula II, R4, R6, R7, R4’, R6’, and R7’ are the same.
In some examples of Formula II, R4, R6, R7, R4’, R6’ and R7’ are all hydrogen, and the compound can be defined by Formula III:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R2 and R3, and/or R2’ and R3’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
with the proviso that when n=0 and m=0, R1, R1’, R3, R5, R3’ and R5’ are not all H and R2 and R2’ are not both phenyl.
In some examples of Formula III, n is 0. In some examples of Formula III, m is 0. In some examples of Formula III, n and m are 0. In some examples of Formula III, n is 1. In some examples of Formula III, m is 1.
In some examples of Formula III, at least one of n and m is 1. In some examples of Formula III, n and m are both 1. In these examples, the compound of Formula III can be defined by Formula IIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R2 and R3, and/or R2’ and R3’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms.
In some examples of Formula IIIa, R1, R1’, R2, R3, R5, R2’, R3’, and R5’ are not all H. In some examples of Formula IIIa, when R1 and R1’ are both–CH3, R2, R3, R5, R2’, R3’, and R5’ are not all H.
In some examples of Formula IIIa, when R1, R1’, R3, R5, R3’, and R5’ are all H, R2 and R2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl,
substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula IIIa, when R1, R1’, R3, R5, R3’, and R5’ are all H, R2 and R2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl. In some examples of Formula IIIa, when R1, R1’, R3, R5, R3’, and R5’ are all H, R2 and R2’ are not both chosen from the moieties shown below.
In some examples of Formula III and Formula IIIa, the compound exhibits C2- symmetry.
In some examples of Formula III and Formula IIIa, R1 and R1’ are the same. In some examples of Formula III and Formula IIIa, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula III and Formula IIIa, R1 and R1’ are both hydrogen. In some examples of Formula III and Formula IIIa, R1 and R1’ are both–CH3.
In some examples of Formula III and Formula IIIa, R2 and R2’ are the same. In some examples of Formula III and Formula IIIa, R2 and R2’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula III and Formula IIIa, R2 and R2’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula III and Formula IIIa, R2 and R2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula III and Formula IIIa, R2 and R2’ are substituted or unsubstituted aryl.
In some examples of Formula III and Formula IIIa, R2 and R2’ are chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula III and Formula IIIa, R2 and R2’ are substituted or unsubstituted phenyl.
In some examples of Formula III and Formula IIIa, R3 and R3’ are the same. In some examples of Formula III and Formula IIIa, R3 and R3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula III and Formula IIIa, R3 and R3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula III and Formula IIIa, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula III and Formula IIIa, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula III and Formula IIIa, R3 and R3’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula III and Formula IIIa, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula III and Formula IIIa, R5 and R5’ are the same. In some examples of Formula III and Formula IIIa, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula III and Formula IIIa, R5 and R5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula III and Formula IIIa, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula III and Formula IIIa, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula III and Formula IIIa, R5 and R5’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula III and Formula IIIa, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula III and Formula IIIa, R3 and R3’ are the same, and R5 and R5’ are the same. In some examples of Formula III and Formula IIIa, R3, R3’, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula III and Formula IIIa, R3, R3’, R5 and R5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In certain examples of Formula III and Formula IIIa, R3, R3’, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula III and Formula IIIa, R3, R3’, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula III and Formula IIIa, R3, R3’, R5 and R5’ are chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula III and Formula IIIa, R3, R3’, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula II, R2, R4, R6, R7, R2’, R4’, R6’ and R7’ are all hydrogen, and the compound can be defined by Formula IV:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula IV, n is 0. In some examples of Formula IV, m is 0. In some examples of Formula IV, n and m are 0. In some examples of Formula IV, n is 1. In some examples of Formula IV, m is 1.
In some examples of Formula IV, at least one of n and m is 1. In some examples of Formula IV, n and m are both 1. In these examples, the compound of Formula IV can be defined by Formula IVa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula IVa, R1, R1’, R3, R5, R3’, and R5’ are not all H.
In some examples of Formula IVa, when R1 and R1’ are both–CH3, R3, R5, R3’, and R5’ are not all H.
In some examples of Formula IV and Formula IVa, the compound exhibits C2- symmetry.
In some examples of Formula IV and Formula IVa, R1 and R1’ are the same. In some examples of Formula IV and Formula IVa, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula IV and Formula IVa, R1 and R1’ are both hydrogen. In some examples of Formula IV and Formula IVa, R1 and R1’ are both–CH3.
In some examples of Formula IV and Formula IVa, R3 and R3’ are the same. In some examples of Formula IV and Formula IVa, R3 and R3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula IV and Formula IVa, R3 and R3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IV and Formula IVa, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IV and Formula IVa, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula IV and Formula IVa, R3 and R3’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In some examples of Formula IV and Formula IVa, R3 and R3’ are
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula IV n F rm la IVa, R3 and R3’ are
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula IV and Formula IVa, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula IV and Formula IVa, R5 and R5’ are the same. In some examples of Formula IV and Formula IVa, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula IV and Formula IVa, R5 and R5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IV and Formula IVa, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IV and Formula IVa, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula IV and Formula IVa, R5 and R5’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula IV n F rm la IVa, R5 and R5’ are
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula IV and Formula IVa, R5 and R5’ are
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula IV and Formula IVa, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula IV and Formula IVa, R3 and R3’ are the same, and R5 and R5’ are the same. In some examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In certain examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula IV and Formula IVa, R3, R3’, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula IVa, the compound can be defined by the formula:
In some examples of Formula IVa, the compound can be defined by the formula:
10 In some examples of Formula II, R2, R4, R5, R6, R7, R2’, R4’, R5’, R6’ and R7’ are all hydrogen, and the compound can be defined by Formula V:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula V, n is 0. In some examples of Formula V, m is 0. In some examples of Formula V, n and m are 0. In some examples of Formula V, n is 1. In some examples of Formula V, m is 1.
In some examples of Formula V, at least one of n and m is 1. In some examples of Formula V, n and m are both 1. In these examples, the compound of Formula V can be defined by Formula Va:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula Va, R1, R1’, R3, and R3’ are not all H.
In some examples of Formula Va, when R1 and R1’ are both–CH3, R3 and R3’ are not both H.
In some examples of Formula V and Formula Va, the compound exhibits C2- symmetry.
In some examples of Formula V and Formula Va, R1 and R1’ are the same. In some examples of Formula V and Formula Va, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula V and Formula Va, R1 and R1’ are both hydrogen. In some examples of Formula V and Formula Va, R1 and R1’ are both–CH3.
In some examples of Formula V and Formula Va, R3 and R3’ are the same. In some examples of Formula V and Formula Va, R3 and R3’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula V and Formula Va, R3 and R3’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula V and Formula Va, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula V and Formula Va, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula V and Formula Va, R3 and R3’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula V and Formula Va, R3 and R3’ are
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula V and Formula Va, R3 and R3’ are
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula V and Formula Va, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula Va, the com ound can be defined by the formula:
In some examples of Formula Va, the com ound can be defined by the formula:
In some examples of Formula II, R2, R3, R4, R6, R7, R2’, R3’, R4’, R6’ and R7’ are all hydrogen, and the compound can be defined by Formula VI:
R5'
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula VI, n is 0. In some examples of Formula VI, m is 0. In some examples of Formula VI, n and m are 0. In some examples of Formula VI, n is 1. In some examples of Formula VI, m is 1.
In some examples of Formula VI, at least one of n and m is 1. In some examples of Formula VI, n and m are both 1. In these examples, the compound of Formula VI can be defined by Formula VIa:
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula VIa, R1, R1’, R5, and R5’ are not all H.
In some examples of Formula VIa, when R1 and R1’ are both–CH3, R3 and R3’ R5’ are not both H.
In some examples of Formula VI and Formula VIa, the compound exhibits C2- symmetry.
In some examples of Formula VI and Formula VIa, R1 and R1’ are the same. In some examples of Formula VI and Formula VIa, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula VI and Formula VIa, R1 and R1’ are both hydrogen. In some examples of Formula VI and Formula VIa, R1 and R1’ are both–CH3.
In some examples of Formula VI and Formula VIa, R5 and R5’ are the same. In some examples of Formula VI and Formula VIa, R5 and R5’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula VI and Formula VIa, R5 and R5’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula VI and Formula VIa, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula VI and Formula VIa, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula VI and Formula VIa, R5 and R5’ are chosen from the moieties shown below
; wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula VI n F rm la VIa, R5 and R5’ are
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula VI and Formula VIa, R5 and R5’ are
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula VI and Formula VIa, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula VIa, the com ound can be defined be the formula:
In some examples of Formula VIa, the compound can be defined be the formula:
3 .
In some examples of Formula II, R3, R4, R5, R6, R7, R3’, R4’, R5’, R6’ and R7’ are all hydrogen, and the compound can be defined by Formula VII:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; with the proviso that when n=0 and m=0, R1 and R1’ are not both H and R2 and R2’ are not both phenyl.
In some examples of Formula VII, n is 0. In some examples of Formula VII, m is 0. In some examples of Formula VII, n and m are 0. In some examples of Formula VII, n is 1. In some examples of Formula VII, m is 1.
In some examples of Formula VII, at least one of n and m is 1. In some examples of Formula VII, n and m are both 1. In these examples, the compound of Formula VII can be defined by Formula VIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula VIIa, R1, R1’, R2, and R2’ are not all H.
In some examples of Formula VIIa, when R1 and R1’ are both–CH3, R2 and R2’ are not both H.
In some examples of Formula VIIa, when R1 and R1’ are both H, R2 and R2’ are not both chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula VIIa, when R1 and R1’ are both H, R2 and R2’ are not both substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl. In some examples of Formula VIIa, when R1 and R1’ are both H, R2 and R2’ are not both chosen from the moieties shown below.
In some examples of Formula VII and Formula VIIa, the compound exhibits C2- symmetry.
In some examples of Formula VII and Formula VIIa, R1 and R1’ are the same. In some examples of Formula VII and Formula VIIa, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula VII and Formula VIIa, R1 and R1’ are both hydrogen. In some examples of Formula VII and Formula VIIa, R1 and R1’ are both–CH3.
In some examples of Formula VII and Formula VIIa, R2 and R2’ are the same. In some examples of Formula VII and Formula VIIa, R2 and R2’ are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula VII and Formula VIIa, R2 and R2’ are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula VII and Formula VIIa, R2 and R2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula VII and Formula VIIa, R2 and R2’ are substituted or unsubstituted aryl.
In some examples of Formula VII and Formula VIIa, R2 and R2’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula VII and Formula VIIa, R2 and R2’ are
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula VII and Formula VIIa, R2 and R2’ are
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halide)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula VII and Formula VIIa, R2 and R2’ are substituted or unsubstituted phenyl.
In some examples of Formula II, R2, R3, R4, R5, R6, R7, R2’, R3’, R4’, R5’, R6’ and R7’ are all hydrogen, and the compound can be defined by Formula VIII:
wherein
n = 0 or 1;
m = 0 or 1; and
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl.
In some examples of Formula VIII, n is 0. In some examples of Formula VIII, m is 0. In some examples of Formula VIII, n and m are 0. In some examples of Formula VIII, n is 1. In some examples of Formula VIII, m is 1.
In some examples of Formula VIII, at least one of n and m is 1. In some examples of Formula VIII, n and m are both 1. In these examples, the compound of Formula VIII can be defined by Formula VIIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl.
In some examples of Formula VIII and Formula VIIIa, the compound exhibits C2- symmetry.
In some examples of Formula VIII and Formula VIIIa, R1 and R1’ are the same. In some examples of Formula VIII and Formula VIIIa, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula VIII and Formula VIIIa, R1 and R1’ are both–CH3. In some examples of Formula VIII, R1 and R1’ are both hydrogen.
In some examples of Formula VIIIa, R1 and R1’ are both hydrogen, and the compound can be defined by the form l
In some examples of Formula VIIIa, R1 and R1’ are both methoxy, and the compound can be defined by the f rm l
In some examples of Formula I, the compound can be defined by Formula IX:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3
, R2’ and R3’, or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula IX, n is 0. In some examples of Formula IX, m is 0. In some examples of Formula IX, n is 1. In some examples of Formula IX, m is 1. In some examples of Formula IX, at least one of n and m is 1. In some examples of Formula IX, n and m are both 1.
In some examples of Formula IX, n and m are both 0. In these examples, the compound of Formula IX can be defined by Formula IXa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted
aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, R2’ and R3’, or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula IX, n is 1 and m is 0. In these examples, the compound of Formula IX can be defined by Formula IXb:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted
thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3
, R2’ and R3’, or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;.
In some examples of Formula IX, Formula IXa, and Formula IXb, R1 and R1’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula IX, Formula IXa, and Formula IXb, R1 and R1’ are both hydrogen. In some examples of Formula IX, Formula IXa, and Formula IXb, R1 and R1’ are both–CH3.
In some examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are substituted or unsubstituted aryl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are substituted or unsubstituted phenyl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are the same. In certain examples of Formula IX, Formula IXa, and Formula IXb, R2 and R2’ are hydrogen.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are hydrogen.
In some examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R5 and R5’ are hydrogen.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5 and R5’ are chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are the same, and R5 and R5’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are hydrogen, and R5 and R5’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R3 and R3’ are the same, and R5 and R5’ are hydrogen.
In some examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5, and R5’ are the same. In some examples of Formula IX, Formula IXa, and Formula IXb, R3, R3’, R5, and R5’ are the hydrogen.
In some examples of Formula IX, Formula IXa, and Formula IXb, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula IX, Formula IXa, and Formula IXb, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula IX, Formula IXa, and Formula IXb, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula IX, Formula IXa, and Formula IXb, R8 and R9 are independently cho n fr m h m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula IX, Formula IXa, and Formula IXb, R8 and R9 are substituted or unsubstituted phenyl.
In some examples of Formula I, the compound can be defined by Formula X:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula X, n is 0. In some examples of Formula X, m is 0. In some examples of Formula X, n is 1. In some examples of Formula X, m is 1. In some examples of Formula X, at least one of n and m is 1. In some examples of Formula X, n and m are both 1.
In some examples of Formula X, n and m are both 0. In these examples, the compound of Formula X can be defined by Formula Xa:
R5'
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula X, n is 1 and m is 0. In these examples, the compound of Formula X can be defined by Formula Xb:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula X, Formula Xa, and Formula Xb, R1 and R1’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula X, Formula Xa, and Formula Xb, R1 and R1’ are both hydrogen. In some examples of Formula X, Formula Xa, and Formula Xb, R1 and R1’ are both–CH3.
In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are hydrogen.
In some examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or
unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R5 and R5’ are hydrogen.
In some examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5 and R5’ are substituted or unsubstituted aryl.
In some examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5 and R5’ are chosen from h m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are the same, and R5 and R5’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are hydrogen, and R5 and R5’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R3 and R3’ are the same, and R5 and R5’ are hydrogen.
In some examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5, and R5’ are the same. In some examples of Formula X, Formula Xa, and Formula Xb, R3, R3’, R5, and R5’ are the hydrogen.
In some examples of Formula X, Formula Xa, and Formula Xb, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula X, Formula Xa, and Formula Xb, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula X, Formula Xa, and Formula Xb, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula X, Formula Xa, and Formula Xb, R8 and R9 are independently chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula X, Formula Xa, and Formula Xb, R8 and R9 are substituted or unsubstituted phenyl.
In some examples of Formula I, the compound can be defined by Formula XI:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XI, n is 0. In some examples of Formula XI, m is 0. In some examples of Formula XI, n is 1. In some examples of Formula XI, m is 1. In some examples of Formula XI, at least one of n and m is 1. In some examples of Formula XI, n and m are both 1.
In some examples of Formula XI, n and m are both 0. In these examples, the compound of Formula XI can be defined by Formula XIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted
aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XI, n is 1 and m is 0. In these examples, the compound of Formula XI can be defined by Formula XIb:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XI, Formula XIa, and Formula XIb, R1 and R1’ are the same. In some examples of Formula XI, Formula XIa, and Formula XIb, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XI, Formula XIa, and Formula XIb, R1 and R1’ are both hydrogen. In some examples of Formula XI, Formula XIa, and Formula XIb, R1 and R1’ are both–CH3.
In some examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XI, Formula XIa, and Formula
XIb, R3 and R3’ are substituted or unsubstituted alkylaryl. In certain examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are substituted or unsubstituted aryl.
In some examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are chosen from the m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are substituted or unsubstituted phenyl.
In some examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are the same. In some examples of Formula XI, Formula XIa, and Formula XIb, R3 and R3’ are hydrogen.
In some examples of Formula XI, Formula XIa, and Formula XIb, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula XI, Formula XIa, and Formula XIb, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In certain examples of Formula XI, Formula XIa, and Formula XIb, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XI, Formula XIa, and Formula XIb, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula XI, Formula XIa, and Formula XIb, R8 and R9 are independently cho n fr m h m i i h n l
In some examples of Formula I, the compound can be defined by Formula XII:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl,
substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XII, n is 0. In some examples of Formula XII, m is 0. In some examples of Formula XII, n is 1. In some examples of Formula XII, m is 1. In some examples of Formula XII, at least one of n and m is 1. In some examples of Formula XII, n and m are both 1.
In some examples of Formula XII, n and m are both 0. In these examples, the compound of Formula XII can be defined by Formula XIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted
cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XII, n is 1 and m is 0. In these examples, the compound of Formula XII can be defined by Formula XIIb:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are the same. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are both hydrogen. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are both–CH3.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are substituted or unsubstituted alkylaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are substituted or
unsubstituted aryl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are chosen from the moieties shown below
; wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are substituted or unsubstituted phenyl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are the same. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R5 and R5’ are hydrogen.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are independently cho n fr m h m i i h n l
In some examples of Formula I, the compound can be defined by Formula XIII:
XIII
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or
unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIII, n is 0. In some examples of Formula XIII, m is 0. In some examples of Formula XIII, n is 1. In some examples of Formula XIII, m is 1. In some examples of Formula XIII, at least one of n and m is 1. In some examples of Formula XIII, n and m are both 1.
In some examples of Formula XIII, n and m are 0. In these examples, the compound of Formula XIII can be defined by Formula XIIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIII, n is 1 and m is 0. In these examples, the compound of Formula XIII can be defined by Formula XIIIb:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or
unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are the same. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are both hydrogen. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R1 and R1’ are both–CH3.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are substituted or unsubstituted alkylaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are substituted or
unsubstituted aryl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are chosen from the moieties shown below
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are the same. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R2 and R2’ are hydrogen.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or
unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are independently cho n fr m h m i i h n l
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XII, Formula XIIa, and Formula XIIb, R8 and R9 are substituted or unsubstituted phenyl.
In some examples of Formula I, the compound can be defined by Formula XIV:
XIV
wherein
n = 0 or 1;
m = 0 or 1; and
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIV, R1 and R1’ are the same. In some examples of Formula XIV, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XIV, R1 and R1’ are both hydrogen. In some examples of Formula XIV, R1 and R1’ are both– CH3.
In some examples of Formula XIV, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted
aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIV, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIV, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XIV, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula XIV, R8 and R9 are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIV, R8 and R9 are substituted or unsubstituted phenyl.
In some examples of Formula XIV, n is 0. In some examples of Formula XIV, m is 0. In some examples of Formula XIV, n is 1. In some examples of Formula XIV, m is 1. In some examples of Formula XIV, at least one of n and m is 1. In some examples of Formula XIV, n and m are both 1.
In some examples of Formula XIV, n and m are both 0. In these examples, the compound of Formula XIV can be defined by Formula XIVa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted
cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVa, R1 and R1’ are the same. In some examples of Formula XIVa, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XIVa, R1 and R1’ are both hydrogen. In some examples of Formula XIVa, R1 and R1’ are both– CH3.
In some examples of Formula XIVa, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVa, R8 and R9 are individually chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVa, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XIVa, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula XIVa, R8 and R9 are independently chosen from the moieties shown be
In certain examples of Formula XIVa, R8 is substituted or unsubstituted phenyl. In certain examples of Formula XIVa, R9 is substituted or unsubstituted phenyl.
In some examples of Formula XIVa, R1 and R1’ are both hydrogen. In these examples, the compound of Formula XIVa can be defined by Formula XIVb:
wherein
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVb, R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVb, R8 and R9 are individually chosen from substituted or
unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVb, R8 and R9 are substituted or unsubstituted alkylaryl. In certain examples of Formula XIVb, R8 and R9 are substituted or unsubstituted aryl.
In some examples of Formula XIVb, R8 and R9 are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula XIVb, R8 is substituted or unsubstituted phenyl. In certain examples of Formula XIVb, R9 is substituted or unsubstituted phenyl.
In some examples of Formula XIVa, R9 is phenyl. In these examples, the compound of Formula XIVa can be defined by Formula XIVc:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVc, R1 and R1’ are the same. In some examples of Formula XIVc, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XIVc, R1 and R1’ are both hydrogen. In some examples of Formula XIVc, R1 and R1’ are both– CH3.
In some examples of Formula XIVc, R8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVc, R8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVc, R8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVc, R8 is substituted or unsubstituted aryl.
In some examples of Formula XIVc, R8 is independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIVc, R8 is substituted or unsubstituted phenyl.
In some examples of Formula XIVa, R1 and R1’ are both hydrogen and R9 is phenyl. In these examples, the compound of Formula XIVa can be defined by Formula XIVd:
XIVd
wherein
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or
unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVd, R8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVd, R8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVd, R8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVd, R8 is substituted or unsubstituted aryl.
In some exam les of Formula XIVd, R8 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIVd, R8 is substituted or unsubstituted phenyl.
In certain examples of Formula XIVd, R8 is phenyl, and the compound can be defined by the formula below.
In some examples of Formula XIV, n is 1 and m is 0. In these examples, the compound of Formula XIV can be defined by Formula XIVe:
R9
R1O Si
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVe, R1 and R1’ are the same. In some examples of Formula XIVe, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XIVe, R1 and R1’ are both hydrogen. In some examples of Formula XIVe, R1 and R1’ are both– CH3.
In some examples of Formula XIVe, R8 and R9 are independently chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVe, R8 and R9 are independently chosen from substituted
or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVe, R8 and R9 are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XIVe, R8 and R9 are independently substituted or unsubstituted aryl.
In some examples of Formula XIVe, R8 and R9 are independently is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIVe, R8 is substituted or unsubstituted phenyl. In certain examples of Formula XIVe, R9 is substituted or unsubstituted phenyl.
In some examples of Formula XIVe, R1 and R1’ are both hydrogen. In these examples, the compound of Formula XIVe can be defined by Formula XIVf:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVf, R8 and R9 are independently chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVf, R8 and R9 are independently chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVf, R8 and R9 are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XIVf, R8 and R9 are independently substituted or unsubstituted aryl.
In some examples of Formula XIVf, R8 and R9 are independently chosen from the moieties shown bel
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIVf, R8 is substituted or unsubstituted phenyl. In certain examples of Formula XIVf, R9 is substituted or unsubstituted phenyl.
In certain examples of Formula XIVe, R9 is phenyl. In these examples, the compound of Formula XIVe can be defined by Formula XIVg:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVg, R1 and R1’ are the same. In some examples of Formula XIVg, R1 and R1’ are both hydrogen or–CH3. In some examples of Formula XIVg, R1 and R1’ are both hydrogen. In some examples of Formula XIVg, R1 and R1’ are both–CH3.
In some examples of Formula XIVg, R8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVg, R8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XIVg, R8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVg, R8 is substituted or unsubstituted aryl.
In some examples of Formula XIVg, R8 is chosen from the moieties shown below
; wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XIVg, R8 is substituted or unsubstituted phenyl.
In certain examples of Formula XIVe, R1 and R1’ are both hydrogen and R9 is phenyl. In these examples, the compound of Formula XIVe can be defined by Formula XIVh:
wherein
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XIVh, R8 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XIVh, R8 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In certain examples of Formula XIVh, R8 is substituted or unsubstituted alkylaryl. In certain examples of Formula XIVh, R8 is substituted or unsubstituted aryl.
In some exam les of Formula XIVh, R8 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula XIVh, R8 is
wherein EDG represents an electron donating group selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl, and p is chosen from 1, 2, 3, 4 and 5.
In some examples of Formula XIVh, R8 is
wherein EWG represents an electron withdrawing group selected from nitro, cyano, and trihalides (e.g., -C(halogen)3), and p is chosen from 1, 2, 3, 4 and 5.
In certain examples of Formula XIVh, R8 is substituted or unsubstituted phenyl. In some examples of Formula XIVh, the compound can be selected from one of the formulas below:
,
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R11, R12, R13, R14, R15, R16, R17, R12’, R13’, R14’, R15’, R16’, and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or
unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R11 and R12, R12 and R13, R13 and R14, R14 and R15, R15 and R16, R16 and R17, R12’ and R13’, R13’ and R14’, R14’ and R15’, R15’ and R16’, or R16’ and R17’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XV, n is 0. In some examples of Formula XV, n is 1. In some examples of Formula XV, R10 and R10’ are the same. In some examples of Formula XV, R10 and R10’ are both hydrogen or–CH3. In some examples of Formula XV, R10 and R10’ are both hydrogen. In some examples of Formula XV, R10 and R10’ are both– CH3.
In some examples of Formula XV, R11 is selected from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R11 is hydrogen.
In some examples of Formula XV, R12 and R12’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R12 is hydrogen. In some examples of Formula XV, R12’ is hydrogen. In some examples of Formula XV, R12 and R12’ are the same. In some examples of Formula XV, R12 and R12’ are both hydrogen.
In some examples of Formula XV, R13 and R13’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R13 is hydrogen. In some examples of Formula XV, R13’ is hydrogen. In some examples of Formula XV, R13 and R13’ are the same. In some examples of Formula XV, R13 and R13’ are both hydrogen.
In some examples of Formula XV, R12, R12’, R13 and R13’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R12, R12’, R13 and R13’ are the same. In some examples of Formula XV, R12, R12’, R13 and R13’ are all hydrogen.
In some examples of Formula XV, R12 and R13 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety
optionally including between 1 and 3 heteroatoms. In some examples of Formula XV, R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
heteroatoms. In some examples of Formula XV, R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XV, R12 and R13 together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XV, R12 and R13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
In some examples of Formula XV, R12’ and R13’ together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XV, R12’ and R13’ together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
heteroatoms. In some examples of Formula XV, R12’ and R13’ together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XV, R12’ and R13’ together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XV, R12’ and R13’ together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
In some examples of Formula XV, R14 and R14’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R14 is hydrogen. In some examples of Formula XV, R14’ is hydrogen. In some examples of Formula XV, R14 and R14’ are the same. In some examples of Formula XV, R14 and R14’ are both hydrogen.
In some examples of Formula XV, R15 and R15’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R15 is hydrogen. In some examples of Formula XV, R15’ is hydrogen. In some examples of Formula XV, R15 and R15’ are the same. In some examples of Formula XV, R15 and R15’ are both hydrogen.
In some examples of Formula XV, R16 and R16’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R16 is hydrogen. In some examples of Formula XV, R16’ is hydrogen. In some examples of Formula XV, R16 and R16’ are the same. In some examples of Formula XV, R16 and R16’ are both hydrogen.
In some examples of Formula XV, R14, R14’, R15, and R15’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R14, R14’, R15,
and R15’ are the same. In some examples of Formula XV, R14, R14’, R15, and R15’ are all hydrogen.
In some examples of Formula XV, R14, R14’, R16, and R16’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R14, R14’, R16, and R16’ are the same. In some examples of Formula XV, R14, R14’, R16, and R16’ are all hydrogen.
In some examples of Formula XV, R15, R15’, R16, and R16’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R15, R15’, R16, and R16’ are the same. In some examples of Formula XV, R15, R15’, R16, and R16’ are all hydrogen.
In some examples of Formula XV, R14, R14’, R15, R15’, R16, and R16’ are
independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XV, R14, R14’, R15, R15’, R16, and R16’ are the same. In some examples of Formula XV, R14, R14’, R15, R15’, R16, and R16’ are all hydrogen.
In some examples of Formula XV, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XV, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XV, R17 and R17’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XV, R17 and R17’ are independently substituted or unsubstituted aryl.
In some examples of Formula XV, R17 and R17’ are independently chosen from the moieties shown bel
In some examples of Formula XV, R18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XV, R18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XV, R18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XV, R18 is substituted or unsubstituted aryl.
In some exam les of Formula XV, R18 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XV, R18 is substituted or unsubstituted phenyl.
In some examples of Formula XV, the compound can be defined by Formula XVa:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R12, R13, R17, R12’, R13’, and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or
unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or
unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R12 and R13, or R12’ and R13’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XVa, n is 0. In some examples of Formula XVa, n is 1.
In some examples of Formula XVa, R10 and R10’ are the same. In some examples of Formula XVa, R10 and R10’ are both hydrogen or–CH3. In some examples of Formula XVa, R10 and R10’ are both hydrogen. In some examples of Formula XVa, R10 and R10’ are both– CH3.
In some examples of Formula XVa, R12 and R12’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVa, R12 is hydrogen. In some examples of Formula XVa, R12’ is hydrogen. In some examples of Formula XVa, R12 and R12’ are the same. In some examples of Formula XVa, R12 and R12’ are both hydrogen.
In some examples of Formula XVa, R13 and R13’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVa, R13 is hydrogen. In some examples of Formula XVa, R13’ is hydrogen. In some examples of Formula XVa, R13 and R13’ are the same. In some examples of Formula XVa, R13 and R13’ are both hydrogen.
In some examples of Formula XVa, R12, R12’, R13 and R13’ are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVa, R12, R12’, R13 and R13’ are the same. In some examples of Formula XVa, R12, R12’, R13 and R13’ are all hydrogen.
In some examples of Formula XVa, R12 and R13 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XVa, R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
heteroatoms. In some examples of Formula XVa, R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVa, R12 and R13 together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVa, R12 and R13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
In some examples of Formula XVa, R12’ and R13’ together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XVa, R12’ and R13’ together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
heteroatoms. In some examples of Formula XVa, R12’ and R13’ together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVa, R12’ and R13’ together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVa, R12’ and R13’ together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
In some examples of Formula XVa, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVa, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain
examples of Formula XVa, R17 and R17’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XVa, R17 and R17’ are independently substituted or unsubstituted aryl.
In some examples of Formula XVa, R17 and R17’ are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XVa, R17 and R17’ are independently substituted or unsubstituted phenyl.
In some examples of Formula XVa, R18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVa, R18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVa, R18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVa, R18 is substituted or unsubstituted aryl.
In some exam les of Formula XVa, R18 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XVa, R18 is substituted or unsubstituted phenyl.
In some examples of Formula XVa, the compound can be defined by Formula XVb:
R17' R17
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R17 and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XVb, n is 0. In some examples of Formula XVb, n is 1.
In some examples of Formula XVb, R10 and R10’ are the same. In some examples of Formula XVb, R10 and R10’ are both hydrogen or–CH3. In some examples of Formula XVb, R10 and R10’ are both hydrogen. In some examples of Formula XVb, R10 and R10’ are both–CH3.
In some examples of Formula XVb, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVb, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVb, R17 and R17’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XVb, R17 and R17’ are independently substituted or unsubstituted aryl.
In some examples of Formula XVb, R17 and R17’ are independently chosen from the moieties shown bel
In some examples of Formula XVb, R18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVb, R18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVb, R18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVb, R18 is substituted or unsubstituted aryl.
In some examples of Formula XVb, R18 is chosen from the moieties shown below
In some examples of Formula XVb, the compound can be defined by the formula:
In some examples of Formula XVa, the compound can be defined by Formula XVc: R17 R17
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R12, R13, R17, and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R12 and R13, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XVc, n is 0. In some examples of Formula XVc, n is 1.
In some examples of Formula XVc, R10 and R10’ are the same. In some examples of Formula XVc, R10 and R10’ are both hydrogen or–CH3. In some examples of Formula XVc, R10 and R10’ are both hydrogen. In some examples of Formula XVc, R10 and R10’ are both– CH3.
In some examples of Formula XVc, R12 is chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVc, R12 is hydrogen.
In some examples of Formula XVc, R13 is chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVc, R13 is hydrogen.
In some examples of Formula XVc, R12 and R13 are independently chosen from hydrogen, hydroxy, and halogen. In some examples of Formula XVc, R12 and R13 are the same. In some examples of Formula XVc, R12 and R13 are both hydrogen.
In some examples of Formula XVc, R12 and R13 together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms. In some examples of Formula XVc, R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3
heteroatoms. In some examples of Formula XVc, R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVc, R12 and R13 together with the atoms to which they are attached, form a 6 membered substituted or unsubstituted cyclic moiety. In some examples of Formula XVc, R12 and R13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
In some examples of Formula XVc, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVc, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVc, R17 and R17’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XVc, R17 and R17’ are independently substituted or unsubstituted aryl.
In some examples of Formula XVc, R17 and R17’ are independently chosen from the moieties shown bel
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XVc, R17 and R17’ are independently substituted or unsubstituted phenyl.
In some examples of Formula XVc, R18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVc, R18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVc, R18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVc, R18 is substituted or unsubstituted aryl.
In some exam les of Formula XVc, R18 is chosen from the moieties shown below
In some examples of Formula XVc, the compound can be defined by Formula XVd:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R17 and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
In some examples of Formula XVd, n is 0. In some examples of Formula XVd, n is 1.
In some examples of Formula XVd, R10 and R10’ are the same. In some examples of Formula XVd, R10 and R10’ are both hydrogen or–CH3. In some examples of Formula
XVd, R10 and R10’ are both hydrogen. In some examples of Formula XVd, R10 and R10’ are both–CH3.
In some examples of Formula XVd, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVd, R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVd, R17 and R17’ are independently substituted or unsubstituted alkylaryl. In certain examples of Formula XVd, R17 and R17’ are independently substituted or unsubstituted aryl.
In some examples of Formula XVd, R17 and R17’ are independently chosen from the moieties shown bel
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XVd, R17 and R17’ are independently substituted or unsubstituted phenyl.
In some examples of Formula XVd, R18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In some examples of Formula XVd, R18 is chosen from substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl. In certain examples of Formula XVd, R18 is substituted or unsubstituted alkylaryl. In certain examples of Formula XVd, R18 is substituted or unsubstituted aryl.
In some examples of Formula XVd, R18 is chosen from the moieties shown below
;
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5. In certain examples of Formula XVd, R18 is substituted or unsubstituted phenyl. Methods of Making
The silane compounds described herein can be prepared using synthetic
methodologies that involve chemical reactions known to one skilled in the art of organic synthesis or variations thereon as appreciated by those skilled in the art. The silane compounds can be prepared from readily available starting materials. Optimum reaction conditions can vary with the particular reactants or solvents used, but such conditions can be determined by one skilled in the art.
Variations on the compounds discussed herein include the addition, subtraction, or movement of the various constituents as described for each compound. Similarly, when one or more chiral centers are present in a molecule, the chirality of the molecule can be changed. Additionally, compound synthesis can involve the protection and deprotection of various chemical groups. The use of protection and deprotection, and the selection of appropriate protecting groups can be determined by one skilled in the art. The chemistry of protecting groups can be found, for example, in Wuts and Greene, Protective Groups in Organic Synthesis, 4th Ed., Wiley & Sons, 2006, which is incorporated herein by reference in its entirety.
The starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, WI), Acros Organics (Morris Plains, NJ), Fisher Scientific (Pittsburgh, PA), Sigma (St. Louis, MO), Pfizer (New York, NY), GlaxoSmithKline (Raleigh, NC), Merck (Whitehouse Station, NJ), Johnson & Johnson (New Brunswick, NJ), Aventis (Bridgewater, NJ), AstraZeneca (Wilmington, DE), Novartis (Basel, Switzerland), Wyeth (Madison, NJ), Bristol-Myers-Squibb (New York, NY), Roche (Basel, Switzerland), Lilly (Indianapolis, IN), Abbott (Abbott Park, IL), Schering Plough (Kenilworth, NJ), or Boehringer Ingelheim (Ingelheim, Germany), or are prepared by methods known to those skilled in the art using
procedures set forth in references such as Fieser and Fieser’s Reagents for Organic
Synthesis, Volumes 1-17 (John Wiley and Sons, 1991); Rodd’s Chemistry of Carbon Compounds, Volumes 1-5 and Supplementals (Elsevier Science Publishers, 1989); Organic Reactions, Volumes 1-40 (John Wiley and Sons, 1991); March’s Advanced Organic Chemistry, (John Wiley and Sons, 4th Edition); and Larock’s Comprehensive Organic Transformations (VCH Publishers Inc., 1989).
Reactions to produce the compounds described herein can be carried out in solvents, which can be selected by one of skill in the art of organic synthesis. Solvents can be substantially nonreactive with the starting materials (reactants), the intermediates, or products under the conditions at which the reactions are carried out (e.g., temperature and pressure). Reactions can be carried out in one solvent or a mixture of more than one solvent.
Product or intermediate formation can be monitored according to any suitable method known in the art. For example, product formation can be monitored by
spectroscopic means, such as nuclear magnetic resonance spectroscopy (e.g., 1H NMR and/or 13C NMR), infrared spectroscopy (e.g., FT-IR spectroscopy), spectrophotometry (e.g., UV-visible spectrometry), mass spectrometry, and/or by chromatography such as high performance liquid chromatography (HPLC) or thin layer chromatography.
By way of example, silane compounds can be prepared from 1,1 '-Bi-2-naphthol (BINOL) or derivatives thereof, as generally illustrated in Scheme 1. Scheme 1. BINOL-Based S nthesis of Silane Com ounds.
Example silane compounds wherein n=m=0 can be prepared using the methodology described in Scheme 2. Starting from BINOL, halogenation using methods known in the art (see, for example, Takaya H et al., Org. Syn. 1989, 67, 20–32) can afford compound 1.1 (dibromobinaphthalene). Compound 1.1 can then be converted to compound 1.2 by treatment with lithium tetramethylpiperidide (LiTMP) and trimethylsilyl chloride (TMSCl), followed by reaction with ICl to form an aryl iodide intermediate, followed by palladium-
catalyzed cross-coupling of the aryl iodide intermediate with phenyl boronic acid. Finally, silacyclization of 1.2 can be accomplished, for example, by lithium halogen exchange (e.g., effected with n-BuLi) followed by treatment with silicon tetrachloride to generate a dichlorosilane mtermediate in situ. The dichlorosilane intermediate can then be hydrolvzed (e.g., by subjection to ether and water) to afford compound 1.3.
Compounds containing 7-membered silacyclic silanediols can also be prepared from BiNOL using methods known in the art. An example strategy for preparing silane compounds wherein n=m=T is illustrated in Scheme 3. BINOL (e.g., (i?)-BINOL) can be triflated (e.g., by treatment with Tf20). Subsequently, a nickel-catalyzed Kumada cross- coupling with MeMgBr can afford provide (i?)-2,2,-dimethyl-l, -binaphthlene.
Deprotonation of both benzyli e methyl groups with n-BuLi/TMED A, followed by quenching with Si(OMe)4, can afford silane compound 3.1. Subsequent hydrolysis with dilute HQ can afford silane compound 3.2.
Scheme 3. Synthetic Route to Example Silane Compounds Including 7-Membered Silacycles.
(a) Tf20, NEt3, CH2CI2, -78°C; (b) NiCl2(dppp), MeMgBr, Ei20; (c) κ-BuLi, TMEDA, Et20, then Si(OMe)4, 0 °C; (d) 1 M HC1 (aq.), Me2CO, 0°C.
Silane compounds containing a variety of substituents at various positions on the binaphthyl back bone can be prepared using modified versions of the methodologies
outlined above. For example, silane compounds including substituents at both the 4, 4’ and 6, 6’ positions can be prepared using the methods outlined in Scheme 4. Drawing from established protocols (see, for example, Hu QS et al., J. Org. Chem. 1999, 64, 7528–7536), (R)-BINOL can be bis-O-hexylated, followed by four-fold bromination and dealkylation with BBr3 to afford compound 4.1. Suzuki-Miyaura cross-coupling with PhB(OH)2, subsequent triflation of the free alcohols, and Nickel-catalyzed Kumada cross-coupling with MeMgBr can provides compound 4.2. Silacyclization can then be performed as described above to prepare the silane compounds. Briefly, deprotonation of both benzylic methyl groups with n-BuLi/TMEDA, followed by quenching with Si(OMe)4, can afford silane compound 4.1. Subsequent hydrolysis with dilute HCl can afford silane compound 4.2
(a) n-CeifeBr, K.2CQ3, MeCN, Δ; (b) Br2, AcOH; (c) BBr3, Π k 78 °C to r.i . (d)
PhB(OH)2, Pd(PPh3)4, K2CO3, THF/H2O, Δ; (e) Tf20, NEt3, CH2CI2, -78 °C to r.t; (f) NiCl2(dppp), MeMgBr, Et20, Δ; (g) «-BuLi, TMEDA, Et20, then Si(OMe)4, 0 °C to r.t.; (h) 1 M HCl (aq.), Me2CO, 0 °C.
By way of example, 6,6'-diphenyl substituted silane compounds can be prepared using a procedure similar to the procedure outlined for preparation of the 4, 4', 6, 6' tetrasubstituted compounds. An example methodology is outlined in Scheme 5. The methodology can involve a regi.o-control.led dibromination of a bis-ethylated ( ?)-BINOL
intermediate at the 6 and 6' positions, followed by a Suzuki-Miyaura cross-coupling proceeding dealkylation to affix substituents at the 6 and 6' positions.
Scheme 5. Synthetic Route to Example Silane Compounds Including Substitnents at the 6 and 6' Positions,
(a) C2H5Br, K2CO3, MeCN, Δ; (b) Br2, CH2Cl2, 0 °C to r.t.; (c) PliB(OH)2, Pd(PPh3)4, K2C03, THF/H2O, Δ; (d) BBr3, CH2Cl2, -78 °C to r.t.; (e) Tf2O, NEt3, CH2C12, "78 °C to r.t.; (f) NiCl2(dppp), MeMgBr, Et2O, Δ; (g) n-BuLi, TMEDA, Et2O, then Si(OMe)4, 0 °C to r.t.; (h) 1 M HC1 faq.), Me2CO, 0 °C. By way of example, 4,4'-diphenyl substituted silane compounds can be prepared using the synthetic methodology outlined in Scheme 6. Using known methods (see, for example, Okuma K et al., Chem. Commun. 2012, 48, 11145–11147), 2- (trimethylsilyl)phenyltriflate can be reacted with benzoylacetone in the presence of CsF to afford 4-phenyl-2-naphthol (compound 6.1). Oxidative coupling with CuTMEDA, followed by resolution with S-(+)-camphorsulfonyl chloride, can provide, after removal of the chiral auxiliary, enantiopure 6.2. As described above, triflation and Nickel-catalyzed Kumada cross-coupling with MeMgBr can afford 6.3; silacycle formation and hydrolysis can afford silane compound 6.4.
Scheme 6. Synthetic Route to Example Silane Compounds Including Substituents at the 4 and 4’ Positions.
Ph
(a) CsF, MeCN; (b) CuTMEDA, CH2Cl2, r.t.; (c) S-(+)-camphorsulfonyl chloride, CH2Cl2, r.t.; (d) MeOH, KOH, 60°C, 20 h; (e) Tf2O, NEt3, CH2Cl2, í 78°C to r.t.; (f) NiCl2(dppp), MeMgBr, Et2O; (g) n-BuLi, TMEDA, Et2O, 0°C to r.t.; (h) 1 M HCl (aq.), Me2CO, 0°C. Methods of Use
The silane compounds described herein can be used as enantioselective
organocatalysts. Accordingly, also provided are catalyst compositions comprising a silane compound described herein.
For example, the silane compounds described herein can be used to catalyze a nucleophilic conjugate addition reaction, in which a first organic species comprising a nitroalkene reacts with a second organic species comprising a nucleophile to provide a product. The silane compounds described herein can also be used to catalyze an acyl-Mannich type reaction in which a first organic species comprising an amine reacts with a second organic species comprising a carbonyl containing compound to provide a product. The silane compounds described herein can also be used to catalyze an epoxide ring opening reaction, in which a first organic species comprising an epoxide reacts with a second organic species comprising a nucelophile to provide a product. In some examples, the silane compounds described herein can be used to catalyze the sequestration of carbon dioxide, in which a first organic species comprising carbon dioxide reacts with a second organic species comprising a reservoir to provide a product. In some embodiments, the silane compounds described herein can be used to catalyze an enantioselective reaction. In these cases, the first organic species reacts with the second organic species to form a chiral product. The product can preferably be enantioentriched.
Methods of using the silane compounds described herein as catalysts can involve contacting the first organic species and the second organic species with a catalytically effective amount of a silane compound or a catalyst composition comprising a silane compound under conditions effective to form the product.
The silane compounds described herein can also be used as sensors for analytes. Examples of suitable analytes include, for example, anions and chiral compounds.
Accordingly, also provided are methods for detecting, identifying, and/or quantifying an analyte in a sample. The methods comprise contacting the sample comprising an analyte with a silane compound described herein; and evaluating an optical property of the silane compound to detect, identify, or quantify the analyte.
By way of example, the silane compounds can exhibit a spectroscopically observable change (e.g., a colorimetric and/or fluorometric response) in the presence of the analyte of interest. In some embodiments, the silane compound can be a luminophore. The spectroscopically observable change can be a change in the absorbance of the silane compound (i.e., color), a change in the fluorescence of the silane compound, a change in the phosphorescence of the silane compound, or a combination thereof.
In these cases, methods for detecting, identifying, and/or quantifying an analyte in a sample can comprise (a) contacting the sample comprising an analyte with a silane compound described herein; and (b) evaluating the optical properties of the silane compound to elucidate the presence of an analyte, to identity an analyte, to determine the concentration of an analyte, or combinations thereof. In certain embodiments, the methods can comprise evaluating the optical properties of the silane compound to determine the concentration of an analyte.
In some cases, one or more spectroscopically observable changes in a silane compound are qualitatively observed to detect the presence of an analyte in a sample. For example, the absorbance of the silane compound (i.e., color) or the fluorescence of the silane compound (under irradiation by, for example a UV blacklight) can be observed by the naked eye to qualitatively assess the presence of an analyte in a sample. In other embodiments, one or more spectroscopically observable changes in a silane compound are measured as part of an assay to quantify the amount of analyte in a sample.
In certain embodiments, the silane compounds can be used in a fluorescence-based assay for the detection and/or quantification of an analyte. Fluorescence assays involve the observation and/or measurement of changes in the fluorescence of a silane compound upon contact with an analyte. The change may take one or more of several forms, including a
change in emission spectra, a change in the intensity of the fluorescence (i.e., fluorescence quantum yield), and a change in the fluorescence lifetime. These changes may be either in the positive or negative direction and may be of a range of magnitudes, which preferably will be detectable as described below.
The emission spectra of a fluorophore sensor can be measured using a
spectrofluorometer. The spectrofluorometer uses a high intensity light source with a particular wavelength (or interval of wavelengths) to excite the fluorophore. The spectrofluorometer then measures the intensity of light emitted by the fluorophore at a range of different wavelengths, called an emission spectra. Changes in the maximum emission wavelength or the shape of the emission spectra that are caused by an analyte of interest in a sample may be used to determine the presence or concentration of the analyte of interest in the sample.
In embodiments where an analyte is detected or quantified by measuring the change in the maximum emission wavelength of the silane compound, the silane compound can be designed to exhibit a large change in maximum emission wavelength upon exposure to the analyte of interest. In some embodiments, the maximum emission wavelength of the silane compound shifts by more than 50 nm, more preferably by more than 75 nm, most preferably by more than 100 nm upon exposure to the analyte of interest.
Changes in the maximum emission wavelength can also be observed with the naked eye, for example with the use of a handheld blacklight, to qualitatively determine the presence of the analyte of interest in a sample.
The fluorescence quantum yield of a silane compound can be measured using methods known in the art. See, for example, Lakowicz, J. R.“Principles of Fluorescence Spectroscopy”, 2nd Ed., Plenum Press, New York, 1999. Generally, the fluorescence quantum yield of the silane compound is obtained by comparison of the integrated area of the corrected emission spectrum of the sensor with that of a reference solution.
A change in the fluorescence quantum yield of the silane compound upon exposure to an analyte of interest may be used as the basis for detecting the presence of the analyte of interest in a sample, and may optionally be used to determine the concentration of the analyte of interest in a sample.
In some embodiments, the silane compound will preferably be selected so as to exhibit a large change in fluorescence quantum yield upon exposure to the analyte of interest. In some embodiments, exposure of the silane compound to the analyte of interest results in at least a 10% reduction in the fluorescence quantum yield of the silane compound
(e.g., at least a 25% reduction in the fluorescence quantum yield of the silane compound, at least a 50% reduction in the fluorescence quantum yield of the silane compound, at least a 75% reduction in the fluorescence quantum yield of the silane compound, or at least a 90% reduction in the fluorescence quantum yield of the silane compound).
In other embodiments, exposure of the silane compound to the analyte of interest can result in at least a 25% increase in the fluorescence quantum yield of the silane compound (e.g., at least a 50% increase in the fluorescence quantum yield of the silane compound, at least a 75% increase in the fluorescence quantum yield of the silane compound, at least a 100% increase in the fluorescence quantum yield of the silane compound, at least a 500% increase in the fluorescence quantum yield of the silane compound, or at least a 1000% increase in the fluorescence quantum yield of the silane compound).
The fluorescence lifetime of a silane compound can also be measured using methods known in the art. Changes in the fluorescence lifetime of a silane compound upon exposure to an analyte can also be used to determine the presence or concentration of an analyte in the sample. EXAMPLES
The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention which are apparent to one skilled in the art.
Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight based on the total weight of the composition in which the component is present, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, temperatures, pressures and other reaction ranges and conditions) that can be used to optimize the product purity and yield obtained from the described process.
Example 1, Chiral Silanediols in Anion-Binding Catalysis
Background
Hydrogen bond donor (HBD) catalysis is evolving as a powerful direction in organic catalysis. Two avenues through which HBD organocatalysts are proposed to operate include the more traditional hydrogen-bonding activation of appropriate functional groups found on electrophiles, and the more recently introduced ion-pairing catalysis. Herein, halide-binding is discussed as a promising new direction for enantioselective silanediol catalysis.
Materials and Methods
General Methods: Diethyl ether, tetrahydrofuran, methylene chloride, and toluene were purified by passage through a bed of activated alumina (Pangborn AB et al.,
Organometallics 1996, 15, 1518-1520). CHCl3 was purchased from Aldrich and used as received. Methanol was freshly distilled from Ca¾. Purification of reaction products was carried out by flash chromatography using Sigma-Aldrich 60 A silica gel (40- 63 μm). Analytical thin layer chromatography was performed on EMD Chemicals 0.25 μm silica gel 60-F254 plates. Visualization was accomplished with UV light and eerie ammonium molybdate stain followed by heating. Melting points (mp) were obtained on a Fisher Scientific Mel-Temp apparatus and are uncorrected. Infrared spectra (IR) were obtained on a Perkin Elmer Spectrum 100R spectrophotometer. Infrared spectra for liquid products were obtained as a thin film on a NaCl disk, and spectra for solid products were collected by preparing a Br pellet containing the title compound. Proton nuclear magnetic resonances (1H NMR) were recorded in deuterated solvents on a Bruker Avance DPX 400 (400 MHz) spectrometer. Chemical shifts are reported in parts per million (ppm, δ) using the solvent as internal standard (CHCb, δ 7.26 and DMSO, δ 2.50). 1H NMR splitting patterns are designated as singlet (s), doublet (d), triplet (t), or quartet (q). Splitting patterns that could not be interpreted or easily visualized are designated as multiplet (m) or broad (br).
Coupling constants are reported in Hertz (Hz). Proton-decoupled carbon (13C NMR) spectra were recorded on a Bruker Avance DPX 400 (100 MHz) spectrometer and are reported in ppm using the solvent as an internal standard (CHCb, δ 77.0; DMSO, δ 39.5). Electrospray mass spectra (ESI-MS) were obtained using a Bruker MicrOTOF Mass Spectrometer.
Unless otherwise noted, all other commercially available reagents and solvents were used without further purification. HPLC analyses were obtained on a Perkin Elmer Series 200 HPLC with multiple wavelength detector.
Preparation of 1: A 250 mL round bottom flask was equipped with a stir bar, flame dried, and placed under N2 atmosphere. A 100 mL pear shape flask was flame dried and placed under N2 atmosphere. The round bottom flask was charged with freshly distilled 1- bromonaphthalene (3.4 mL, 24.4 mmol) and 100 mL of dry Et2O. The solution was stirred and cooled to -78°C. The pear shape flask was charged with 20 mL of dry Et2O and SiCl4 (1.4 mL, 12.2 mmol). A solution of n-BuLi in hexanes (1.5 M, 17.9 mL, 26.8 mmol) was added to the 1-bromonaphthalene/Et2O solution dropwise with stirring at -78°C to afford an off white suspension. The cold bath was removed and the mixture was allowed to warm to 23ºC over an hour. The mixture was recooled to -78ºC and the SiCl4/Et2O solution was added dropwise with stirring to afford a clear, light yellow solution. The yellow solution was stirred overnight allowing it to come to 23°C. The mixture was concentrated to afford a yellow oil with a white ppt. About 50 mL of Et2O and 9 mL of H2O were added to the oil and this mixture was stirred at 23°C for 2 h. Saturated NaHCO3 (aq) was added to neutralize the mixture to pH 7. This solution was extracted with Et2O/brine, concentrated, and dried over Na 2 SO 4 to afford a light yellow oil which was crystallized from Et 2 O/hexanes to afford a white powder which was washed twice with hexanes (2.89 g, 67%). 1H NMR (400 MHz, CDCb) δ 8.34 id. J = 8.0 Hz, 2H); 8.00 (dd, J 8.0 Hz, 1.2 Hz, 21 ! }: 7.94 (d, ./ 8.4 Hz, 2H); 7.86 (dd, J = 8.4 Hz, 1.2 Hz, 2H); 7.48–7.40 (m, 6H). All spectral data matched that previously reported (Schafer AG et al., Org. Lett. 2011, 13, 5228–5231). Scheme 7. Preparation of Binaphthyl-Derived Silanediol
(R)-Trifluoro-methanesulfonic acid 2’-trifluoromethanesulfonyloxy [1,1’] binapthalenyl-2-yl ester: A 500 mL round bottom flask was equipped with a stir bar, flame dried, placed under N2 atmosphere, charged with R-(+)-BINOL (10.00 g, 35.0 mmol) and CH2Cl2 (145 mL), and was cooled to–78ºC. Et3N (12.2 mL, 87.5 mmol, 2.5 equiv) freshly
distilled from CaH2 was then added dropwise. This mixture was stirred at–78ºC for 5 min, and Tf2O (14.6 mL, 86.8 mmol, 2.5 equiv) was added dropwise at–78ºC. This solution was stirred overnight while warming to 23ºC. The resulting black solution was then cooled to 0ºC, and 10 mL 1 M HCl(aq) was added. The organic layer was separated, and the aqueous layer was extracted 3 times with CH2Cl2. The organic layers were combined, washed with saturated NaHCO3 (aq), dried with Na2SO4, and concentrated to afford a thick black oil. The oil was passed through a short silica gel plug using 90/10 hexanes/EtOAc as the eluent. The resulting off white solid was recrystallized from 15 mL of hexanes to afford a flaky, white product (18.68 g, 33.9 mmol, 97%). XH NMR (400 MHz, CDCI3) δ 8.15 (d, J= 9.2 Hz, 2H); 8.01 (d, J = 8 Hz, 2H); 7.62 (d, J = 9.2 Hz, 2H); 7.59 (ddd, J = 8.4 Hz, 7.2 Hz, 1.2 Hz, 2H); 7.41 (ddd, J = 8.4 Hz, 7.2 Hz, 1.2 Hz, 2H); 7.25 (d, J = 8.4 Hz, 2H). All spectral data matched that previously reported (Bulman Page PC et al., Org. Lett. 2004, 6, 1543– 1546).
(R)-2,2’-Dimethyl-1,1’-binaphthyl (11): A 250 mL 2-necked round bottom flask was equipped with a stir bar, flame dried, placed under N2 atmosphere, and charged with (R)-Trifluoromethanesulfonic acid 2’-trifluoromethanesulfonyloxy [1,1’]binapthalenyl-2-yl ester (12.83 g, 23.3 mmol). Dry Et2O (160 mL) was added, followed by Ni(dppp)Cl2 (631 mg, 1.16 mmol, 0.05 equiv.). The mixture was cooled to 0ºC and MeMgBr (36 mL, 3.0 M, 108 mmol, 4.6 equiv) was added dropwise with stirring. The mixture became clear and yellow during the addition, and after complete addition of the MeMgBr, was refluxed overnight. The solution became black, and after complete conversion by TLC, was carefully poured into ice-cooled 1 M HCl(aq). The reaction was filtered through a pad of celite, the layers separated, and the aqueous layer extracted 3 times with Et2O. The organic layers were combined, dried with Na2SO4, and concentrated to afford an off-white oil. The oil was passed through a short silica gel plug using hexanes as the eluent to afford a white powder upon concentration (6.49 g, 22.9 mmol, 98%). ¾ NMR (400 MHz, CDCI3) δ 7.90 (d, J= 8.4 Hz, 2H); 7.88 (d, J = 8 Hz, 2H); 7.51 (d, J = 8.4 Hz, 2H); 7.39 (ddd, J = 8.4 Hz, 7.2 Hz, 1.2 Hz, 2H); 7.21 (ddd, J = 8.4 Hz, 6.9 Hz, 1.3 Hz, 2H); 7.05 (d, J = 8.0 Hz, 2H); 2.04 (s, 6H). All spectral data matched that previously reported (Bulman Page PC et al., Org. Lett. 2004, 6, 1543–1546).
4,4-dimethoxy-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]silepine (4): Adapting a procedure by Oestreich (Mewald M et al., Chem. Eur. J. 2011, 17, 9406–9414), a 100 mL round bottom flask was equipped with a large stir bar, flame dried, and placed under N2 atmosphere. The flask was charged with a solution of n-BuLi in hexanes (8.9 mL, 1.2 M,
10.7 mmol, 3.0 equiv) and cooled to 0ºC. 11 (990 mg, 3.51 mmol) was added in dry Et2O (8 mL) dropwise. This solution was stirred at 0ºC for 5 min, then N,N,N’,N’- tetramethylethylenediamine (TMEDA, 1.6 mL, 10.7 mmol, 3.0 equiv) previously distilled from CaH2 was added dropwise at 0ºC. The resulting yellow solution was allowed to come to 23ºC, and was stirred for 24 h after complete addition of TMEDA. The now very dark red n-BuLi/TMEDA/binaphthalene mixture was cooled to 0ºC, and distilled Si(OMe)4 (2.0 mL, 13.6 mmol, 3.9 equiv) in Et2O (8 mL) was added dropwise. The mixture was allowed to come to 23ºC and stirred overnight to afford an opaque yellow mixture. This mixture was filtered through celite using Et2O (80 mL) and CH2Cl2 (20 mL) to afford a clear, neon green solution. The solution was concentrated, diluted in 5 mL CH2Cl2, and quickly run through a short silica gel plug packed with hexanes using 1500 mL of 80/20 hexanes/EtOAc as the eluent. The eluent was concentrated to afford a yellow oil which was placed under an Ar atmosphere. The crude mixture stood undisturbed under Ar for 24 h, during which time clear, colorless crystals formed. After 24 h, the crystals were carefully triturated with 3 x 3 mL portions of hexanes to afford 396 mg of the desired silacycle (1.07 mmol, 31%). After trituration, a small amount of silacycle with an ethoxy group and a methoxy group was left, presumably from the cleavage of Et2O during the course of the lithiation (Jung ME, Hogan KT, Tetrahedron Lett. 1988, 29, 6199–6202). This was carried through to the hydrolysis step. R/= 0.51 (4:1 hexanes/EtOAc); mp 197-202°C; IR (KBr) 3055, 2936, 2834, 1307, 1185, 1149, 1092 cm-1; XH NMR (400 MHz, CDCb) 6 7.88 (d, J= 8.4 Hz, 2H); 7.87 (d, J= 8.4 Hz, 2H); 7.47 (d, J - 8.4 Hz, 2H); 7.36 (ddd, J - 8.0 Hz, 6.8 Hz, 1.2 Hz, 2H); 7.17 (ddd, J= 8.0 Hz, 6.8 Hz, 1.2 Hz, 2H); 7.07 (d, J= 7.4 Hz, 2 H); 3.50 (s, 6H); 2.22 (d, J= 14 Hz, 2 H), 2.08 (d, J- 14.0 Hz, 2H). 13C NMR (100 MHz, CDCb) δ 134.4, 132.8, 132.7, 131.8, 128.3, 128.1, 128.0, 126.4, 125.9, 124.5, 50.9, 19.9; HRMS (ESI): Mass calculated for C24H2202SiNa [M+Naf, 393.1281. Found [M+Na]+, 393.1264. [α]¾ = -195.2 (c 0.985, CHCI3).
3H-dinaphtho[2,1-c:1',2'-e]silepine-4,4(5H)-diol (3): Adapting a procedure by Tacke (Tacke R et al., Organometallics 2004,23, 4915–4923), a 250 mL round bottom flask was equipped with a stir bar, placed under N2 atmosphere, and charged with 4 (378.0 mg, 1.02 mmol). ACS grade acetone (40 mL) was added and the solution was cooled to 0ºC. Freshly prepared 1 M HCl (aq) (10 mL) was added to the solution dropwise at 0ºC. The solution was stirred at 0ºC until TLC showed complete consumption of starting material, generally within 1–2 h. Et2O (50 mL) was added at 0ºC, followed by saturated NaHCO3 slowly until pH 7 was achieved. The mixture was shaken vigorously, the layers were
separated, and the aqueous layer extracted 3 times with Et2O, checking to ensure pH 7 is maintained throughout the extraction. The organic layers were combined, dried with Na2SO4, and concentrated to afford a white powder (364 mg, 94%) as a 2:1 complex with Et2O. This compound was used directly as the Et2O complex, taking into account the residual solvent when calculating catalyst loadings. Rf = 0.28 (1:1 hexanes/EtOAc), will significantly tail; IR (KBr) 3401, 3051, 2969, 1232, 1143, 912, 822, 837 cm-1; 1H NMR (400 MHz, CDCb) δ 7.88 (d, J= 8.4 Hz, 4H); 7.47 (d, J= 8.4 Hz, 2H); 7.37 (ddd, J= 8.4 Hz, 6.8 Hz, 1.2 Hz, 2H); 7.18 (ddd, J = 10 Hz, 6.8 Hz, 1.2 Hz, 2H); 7.09 (d, J = 7.6 Hz, 2 H); 2.18 (d, J = 14 Hz, 2 H), 2.12 (d, J = 14.0 Hz, 2H). 13C NMR (100 MHz, CDCl3) 134.5, 132.9, 132.8, 132.0, 128.6, 128.2, 128.0, 126.6, 126.2, 124.8, 23.4; HRMS (ESI): Mass calculated for C22H1802SiNa [M^Naf, 365.0968. Found [M^Niaf, 365.0974. [a]24 D = -280.3 (c 0.90, CHCl3).
General Procedure for Titration of Silane Diol 3 and 4 with
Tetrabutylammonium Chloride: A solution of R-3 (5.0 x 10-3 M) in CDCl3 was prepared in a 2 mL volumetric flask. Portions of TBACl were quantitatively transferred to the flask and 1H NMR spectra of the solutions were recorded after the addition of each equivalent, ensuring that the concentration of R-3 did not change.
Confirmation that the O–H peak was shifting was achieved by washing a solution of R-3 in CDCl3 with D2O, drying the sample with Na2SO4, and recording the NMR spectrum, which lacks the peak at 2.4 ppm. No changes in methylene or aromatic proton resonances were observed during the TBACl titration of 4. General Procedure for Silanediol Catalyzed Acyl-Mannich Reactions Scheme 8. General Procedure for Silanediol Catalyzed Acyl-Mannich Reactions
General Procedure for Table 1
(9a): An oven dried 2-dram vial with screw top cap and septa was equipped with a stir bar and flushed with argon. The vial was sealed and covered further with parafilm. Isoquinoline (11.8 uL, 0.1 mmol, 1.0 equiv) was added via syringe, solvent (2 mL) was added and the solution was cooled to 0 °C. 2,2,2-Trichloroethyl chloroformate (15.0 μί,
0.11 mmol, 1.1 equiv) was added, the ice bath was removed and the solution was warmed to room temperature while stirring for 30 minutes. The cloudy suspension was cooled to–78ºC and catalyst (0.02 mmol, 0.2 equiv) was added as a solution in solvent followed by 8-TBS (33 mg, 0.15 mmols, 1.5 equiv). The reaction vessel was transferred to a–78ºC acetone bath equipped with immersion cooling coil and stirred for 40 hours. The reaction was quenched at–78 ºC by the addition of NaOMe (0.2 ml, 0.5 M in MeOH, 1.0 equiv) and then warmed to room temperature before filtration through a short silica gel plug with EtOAc as the eluent. Removal of the solvent in vacuo and subsequent purification via flash column chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes) yielded the title compound as a colorless oil. 1H NMR (400 MHz, CDCl3): the compound exists as a 3:1 mixture of carbamate rotamers. Signals corresponding to the major rotamer: δ 7.28-7.19 (m, 2H), 7.10-6.95 (m, 2H), 6.96 (d, J- 7.6 Hz, 1H), 5.95 (d, J= 7.6 Hz, 1 H), 5.74 (s, lH), 4.97 (d, J= 12.0 Hz, lH), 4.70 (d, J= 12.0 Hz, 1H), 3.64 (s, 3H), 1.20 (s, 3H), 1.12 (s, 3H). Representative signals of the minor rotamer: δ 6.05 (d, J= 7.6 Hz, 1H), 5.79 (s, 1H), 4.86 (s, 2H), 3.61 (s, 3H), 1.29 (s, 3H), 1.26 (s, 3H). 13C NMR. (100 MHz, CDCI3) Signals correspond to major rotamer: δ 175.9, 152.3, 131.3, 128.4, 128.0, 127.2, 125.6, 124.9, 112.0, 95.2, 75.7, 60.9, 52.2, 50.3, 22.6, 21.5. IR (neat) 2991, 2924, 2357, 2343, 1724, 1717, 1627, 1448, 1374, 1322, 1225, 1128, 1046, 941 cm 1; HRMS (ESI): Mass Calculated for C17H18Cl3N04 [M÷Na]+, 428.0199. Found [M+Na]+, 428.0189.
General Procedure for Table 2
(9a) Table 2, entry 1 : An oven dried 2-dram vial with screw top cap and septa was equipped with a stir bar and flushed with argon. The vial was sealed and covered further with parafilm. Isoquinoline (11.8 μL, 0.1 mmol, 1.0 equiv) was added via syringe, PhMe (2 mL) was added and the solution was cooled to 0°C. 2,2,2-Trichloroethyl chloroformate
(15.0 μ-L, 0.11 mmol, 1.1 equiv) was added, the ice bath was removed and the solution was warmed to room temperature while stirring for 30 minutes. The cloudy suspension was cooled to -78°C. R-(3) (6.8 mg, 0.02 mmol, 0.2 equiv) was added as a solution in PhMe followed by methyl trimethylsilyl dimethylketene acetal 8-TMS (30.5 μL,, 0.15 mmols, 1.5 equiv). The reaction vessel was transferred to a -78°C acetone bath equipped with immersion cooling coil and stirred for 40 hours. The reaction was quenched at -78°C by the addition of NaOMe (0.2 ml, 0.5 M in MeOH, 1.0 equiv) and then warmed to room temperature before filtration through a short silica gel plug with EtOAc as the eluent.
Removal of the solvent in vacuo and subsequent purification via flash column
chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes) yielded the title compound as a colorless oil (32.4 mg, 0.080 mmols, 80% yield). All spectral data matched spectra for 9a as reported above. (Rf = 0.45 in 10:90 EtOAc:Hexanes),
enantiomeric excess was found to be 8% by chiral HPLC (Chiralpak OD-H, 1%
isopropanol/99% hexane 0.7 mL/min, tr (minor): 12.8 min, tr (major): 15.7 min.; Figure 1 ) >Į @24
D =–24.5 (c 1.11, CHCl3).
(9a) Table 2, entry 2: The general procedure was repeated with 8-TBS as the nucleophile. All spectral data matched spectra for 9a as reported above. Purification via flash column chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes) yielded the title compound as a colorless oil (28.9 mg, 0.071 mmols, 71% yield) (Rf = 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was found to be 18% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (minor): 13.3 min, tr (major): 16.2 min.; Figure 2) >Į @24
D =–57.4 (c 0.63, CHCl3).
(9a) Table 2, entry 3: The general procedure was repeated with 8-TIPS as the nucleophile. All spectral data matched spectra for 9a as reported above. Purification via flash column chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96
EtOAc:Hexanes), subsequent concentration under reduced pressure and filtration through a plug of activity II neutral alumina with CH2Cl2 to remove TIPSOH, yielded the title compound as a colorless oil (22.4 mg, 0.055 mmols, 55% yield) (Rf = 0.45 in 10:90
EtOAc:Hexanes), enantiomeric excess was found to be 28% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (minor): 12.8 min, tr (major): 15.6 min.; Figure 3) >Į @24
D =–128.2 (c 0.60, CHCl3).
(9a) Table 2, entry 4: The general procedure was repeated with 8-TIPS as the nucleophile as well as 100 mol% R-(3) (34.2 mg, 0.10 mmol). All spectral data matched spectra for 9a as reported above. Purification via flash column chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes), subsequent concentration under reduced pressure and filtration through a plug of activity II neutral alumina with CH2Cl2 to remove TIPSOH, yielded the title compound as a colorless oil (30.2 mg, 0.074 mmols, 74% yield) (Rf = 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was found to be 28% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (minor): 14.1 min, tr (major): 17.7 min., Figure 4) >Į @24
D =–128.2 (c 1.00, CHCl3).
(9b) Table 2, entry 5: The general procedure was repeated with 8-TIPS as the nucleophile. Purification via flash column chromatography on silica gel (0:100 ethyl acetate:hexanes to 4:96 ethyl acetate hexanes), subsequent concentration under reduced
pressure and filtration through a plug of activity II neutral alumina with CH2Q2 to remove TIPSQH, yielded the title compound as a colorless oil (27.7 mg, 0.057 mmols, 57% yield) (R/ = 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was determined to be 26% by chirai HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, ir(minor): 12.5 min, ir(major): 18.3 min.; Figure 5) [a]24 D = -54.3° (c 0.96, CHCI3). lR NMR (400 MHz, CDCb): the compound exists as a 3 : 1 mixture of carbamate rotamers. Signals
corresponding to the major rotamer: 6 7.49 (dd, J = 7.6 Hz, 1.6 Hz, 1H), 7, 10-7.00 (m, 3H), 6.33 id. J 8.0 Hz, 1H ). 5.70 (s, 1H ). 4.98 (d. ./ 12.0 Hz, 1H ). 4.71 id. ./ 12.0 Hz, 1H ). 3.62 (s, 3H), 1.19 (s, 3H), 1.12 (s, 3H). Representative signals of the minor rotamer: δ 6.43 (d, J = 12.0 Hz, 1H ), 5.74 (s, 1H ), 4.86 (s, 21 1 ). 3.60 (s, 31 1 ). 1 .28 (s, 31 1 ). 1 .25 (s, 31 1 ). i3C NMR (100 MHz, CDCI3) Signals correspond to major rotamer: δ 175.5, 152.0 132.4, 130.7, 130.0, 127.9, 127.1, 120.4, 110.4, 75.6, 60.9, 52.2, 50.1, 22.7, 21.5. IR (neat) 3110, 2976, 2946, 2357, 2335, 1724, 1627, 1553, 1441 1381, 1322, 1269, 1120, 770, 718 cm-1; HRMS (ESI): Mass Calculated for C17H17BrCl3NO4 [M+Na]+, 505.9304. Found [M+Na]+,
505.9299.
(9b) Table 2, entry 6: The general procedure was repeated with 8-TBS as the nucleophile. All spectral data matched spectra for 9b as reported above. Purification via flash column chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes) yielded the title compound as a colorless oil (32.1 mg, 0.066 mmols, 66% yield) (Rf = 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was found to be 18% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (minor): 14.5 min, tr (major): 22.2 min.; Figure 6) >Į @24
D = -44.5 (c 1.85, CHCl3).
(9c) Table 2 entry 7: The general procedure was repeated with 8-TIPS as the nucleophile. Purification via flash column chromatography on silica gel (0:100 ethyl acetate:hexanes to 5:95 ethyl acetate hexanes) yielded the title compound as a colorless oil (26.9 mg, 0.061 mmols, 61% yield) (Rf = 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was determined to be 32% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr(minor): 11.4 min, tr(major): 17.0 min.; Figure 7) >Į @24 D–71.3º (c 0.99, CHCl3).1H NMR (400 MHz, CDCl3): the compound exists as a 3:1 mixture of carbamate rotamers. Signals corresponding to the major rotamer: 6 7.31 (dd, J:::: 8.0, 1.2 Hz, 1H), 7.13 (t, J= 8.0 Hz, 1H), 7.06 (d, J = 8.0 Hz, lH), 6.98 (app d, J = 8.0 Hz, lH), 6.35 (d, J 7.6 Hz, 1 H), 5.72 (s, 1 H), 4.98 (d, J -- 12.0 Hz,) 4.71 (d, J = 12,0 Hz, 1H), 3.63 (s, 3H),
1.20 (s, 3H), 1.12 (s, 3H). Representative signals of the minor rotamer: δ 6.45 (d, J = 12.0 Hz, I I I ), 5.76 (s, I I I ). 4.87 (s, 21 1 ). 3.61 (s, 3H), 1.29 (s, 3H), 1.26 (s, 3H). 13C NMR (100
MHz, CDCI3) Signals correspond to major rotamer: δ 175.5, 152.0, 129.9, 129.1, 127.6, 126.9, 126.4, 125.7, 107.9, 94.9, 75.6, 60.7, 52.1, 50.1, 29.7, 22.6, 21.4. IR (neat) 2984, 2946, 1724, 1627, 1553, 1448, 1381, 1120, 770 cm'1; HRMS (ESI): Mass Calculated for C17H17C14N04 [M ]+, 461.9809. Found [MTs[a]+, 461.9804.
(9c) Table 2 entry 8: The general procedure was repeated with 8-TBS as the nucleophile. All spectral data matched spectra for 9c as reported above. Purification via flash column chromatography on silica gel (0:100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes) yielded the title compound as a colorless oil (35.2 mg, 0.080 mmols, 80% yield) (I = 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was found to be 20% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (minor): 13.3 min, tr (major): 20.5 min.; Figure 8) [a]24 D = -58.1 (c 1.57, CHCI3).
(9d) Table 2 entry 9: The general procedure was repeated with 8-TIPS as the nucleophile. Purification via flash column chromatography on silica gel (0:100 diethyl ethenhexanes to 15:85 diethyl ethenhexanes) yielded the title compound as a bright yellow oil (29.5 mg, 0.065 mmols, 65% yield) (I = 0.16 in 20:80 Et20:Hexanes), enantiomeric excess was determined to be 17% by chiral HPLC (Chiralpak OD-H, 4% isopropanol/96% hexane 0.7 mL/min, fr(major): 15.7 min, /r(minor): 22.1 min.; Figure 9) [a]24 D = +26.1 (c 0.91, CHCI3) XH NMR (400 MHz, CDCI3): the compound exists as a 4:1 mixture of carbamate rotamers. Signals corresponding to the major rotamer: δ 7.94 (dd, J= 7.2, 2.4 Hz, 1H), 7.40-7.30 (m, 2H), 7.18 (d, J= 8.0 Hz, 1H), 6.70 (d, J= 8.4 Hz, 1H), 5.77 (s, 1H),
5.00 (d, J = 11.6 Hz, 1H), 4.73 (d, J- 11.6 Hz, 1H), 3.63 (s, 3H), 1.21 (s, 3H), 1.16 (s, 3H). Representative signals of the minor rotamer: δ 6.79 (d, J= 8.4 Hz, 1H), 4.88 (s, 2H), 1.29 (s, 3H), 1.26 (s, 3H). 13C NMR (100 MHz, CDCI3) Signals correspond to major rotamer: δ 175.1, 151.7, 144.8, 132.8, 130.4, 129.5, 126.7, 125.9, 124.8, 105.8, 94.7, 75.7, 60.84, 52.3, 49.9, 22.8, 21.5 IR (neat) 2954, 2924, 2857, 1724, 1627, 1515, 1456, 1381, 1329, 1262, 1120, 897 cm"1; HRMS (ESI): Mass Calculated for C17Hi7Cl4N04 [M+Na]+, 473.0050. Found pVTNaf, 473.0044.
(9d) Table 2 entry 10: The general procedure was repeated with 8-TBS as the nucleophile. All spectral data matched spectra for 9d as reported above. Purification via flash column chromatography on silica gel (0:100 diethyl ethenhexanes to 15:85 diethyl ethenhexanes) yielded the title compound as a colorless oil (32.7 mg, 0.072 mmols, 72% yield) (R/^ 0.45 in 10:90 EtOAc:Hexanes), enantiomeric excess was found to be 50% by chiral HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (major): 16.2 min, tr (minor): 23.0 min.; Figure 10) [a]24 D = +70.1 (c 1.60, CHCI3).
Preparation of Racemic Samples for HPLC Analysis: in an oven dried 2 -dram vial with stir bar, a solution of the appropriate isoquinoline (0.1 mmol) in 2 mL
dichloromethane was prepared and cooled to 0 °C. 2,2,2-Trichloroethyl chloroformate (15.0 μΐ., 0.1 1 mmol, 1.1 equiv) was added, the ice bath was removed and the solution was warmed to room temperature while stirring for 30 minutes. The reaction was then cooled to - 78°C and the appropriate silyl ketene acetal (0.15 mmol 1 .5 equiv) was added. The reaction was allowed to warm to room temperature and stir overnight (14-18 bis). The products were isolated under the same column conditions as their enantioenriched counterparts (see Figure 1 1 , Figure 12, Figure 13, and Figure 14 for racemic samples of 9a, 9b, 9c, and 9d, respectively).
Synthesis of Bis(TMS) Derivative of Si!asiedio! R~3 (3H-dinaphtho[2,l-c:l',2'- e]siIepis¾e~4,4(5M)~diol) for H PLC Analysis (Scheme 9) Scheme 9. Synthesis of Bis(TMS) Derivative of 3H-dinaphtho[2,l-c: l',2'-e]siIepine- 4,4(5H)-dio! for HPLC Analysis
A 25 mL round bottom flask equipped with a Teflon coated magnetic stir bar was flame dried under vacuum and purged with nitrogen gas. The flask was then fitted with a rubber septa and placed under argon atmosphere. The flask was then charged with (R)-3 (27.4 mg, 0.08 mrnois, 1 .0 equiv) followed by THF (0.27 ml,). NEt3 (40 μΐ,, 0.32 mmols, 4.0 equiv) was added to the reaction mixture via syringe, followed by TMSC1 (22 μΐ., 0.17 mmols, 2.2 equiv). The reaction stirred at room temperature for 12 hours, then diluted with 15 mL of diethyl ether and washed with water (10 mL), saturated sodium bi carbonate (2 x 10 mL), and brine (2 10 mL), The organic layer was dried with anhydrous sodium sulfate, and the solvent was removed in vacuo resulting in a clear yellow oil. Purification via flash column chromatography on silica gel (100% hexanes as eluent) yielded the title compound as a white solid ( 18.3 mg, 0.038 mmols, 48% yield) (R/ ;=: 0.30 in 99: 1 Hexanes:EtOAc), enantiomeric excess was determined to be >99% by cbiral HPLC (Chiralpak OD-H, 100% hexane 0.5 mL/rnin, rr(minor): 1 1 .2 min, fr(major): 15.7 min.; Figure 15; see also Figure 16 for racemic sample) [cx]24 D = -155.9° (c 1.01 , CHCls). Ή NMR (400 MHz, CDCI3): δ 7.87
(d, J = 8.4 Hz, 2H), 7.84 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H), 7.35 (ddd, J = 8.0, 6.8, 1.2 Hz, 2H), 7.16 (ddd, J = 8.8, 6.8, 1.2 Hz, 2H), 7.09 (d, J = 8.8 Hz, 2H), 2.00 (d, J = 13.6 Hz, 2H), 1.96 (d, J = 13.6 Hz, 2H), 0.02 (s, 18H). 13C NMR (100 MHz, CDCl3@@į@ 135.7, 132.8, 132.7, 131.8, 128.4, 128.1, 128.0, 126.7, 125.8, 124.3, 24.5, 2.0. IR (KBR) 3049, 2946, 2898, 1500, 1395, 1250, 1147, 1067 (br), 917, 837, 750, 735 cm-1. Mass Calculated for C28H34O2Si3 [M+Na]+, 509.1764. Found [M+Na]+, 509.1766. Synthesis of Silyl Ketene Acetals (Scheme 10) Scheme 10. Synthesis of Silyl Ketene Acetals
NMR (400 MHz, CDCl3): 6 3.56 (s, 3H), 1.57 (s, 6H), 1.09-1.18 (m, 21H). All spectral data
matched that previously reported (Liu SY et al., J. Am. Chem. Soc. 2Θ05, 127, 15352- 15353).
te/Y-Butvl((l-methoxv-2-methvlprop-l -en-l-vi)oxv)dimethyls¾^ (8-TBS): Using the method reported by the Jacobsen group (Wenzel AG, Jacobsen EN, J. Am. Chem. Soc. 20Θ2, 124, 12964-12965), the title compound (4.04 g, 18.7 mmol, 75% yield) was obtained as a clear colorless liquid. "Ή NMR (400 MHz, CDCh): δ 3.51 (s, 3H), 1.57 (s, 3H), 1.53 (s, 3H), 0.96 (s, 9H), 0.14 (s, 6H). All spectral data matched that previously reported
(Sehaeckel R. et al., Angew. Chem. Int. Ed. 2010, 49, 1 619-1622).
terr-butyl(( 1 -isopropoxy vmyl)oxy)dimethylsilane (S 1 ) i Following the same procedure as above, the title compound was prepared on a 30 mmol scale to yield the title compound (5.24 g, 24.2 mmol, 81 % yield) as a clear colorless liquid. SH NMR (400 MHz, CDCI3): δ 4.19 (sep, J ------- 6.4 Hz, 1 H), 3.27 (d, J= 2.4 Hz, ! H), 3.08 (d, J= 2.4 Hz, i l l ),
1.25 (d, J = 6.4 Hz, 6H), 0.93 (s, 9H), 0.17 (s, 6H). All spectral data matched that previously reported (Wenzel AG, Jacobsen EN, J. Am. Chem. Soc. 2002, 124, 12964- 12965).
Tentative Assignment of Absolute Stereochemistry (Scheme Π)
Scheme 11. Tentative assignment of absolute stereochemistry
2.2.2-i; it'h loroeihyi (S)- 1 ~i 2-isop; opoxy-2-uxocihyl )j^ocnsinolinc-2( "1 / j-carboxylaic (S2): Using the same general procedure for silanediol catalyzed acyl-Mannich reactions above, the title compound was purified via flash column chromatography on silica gel (0: 100 EtOAc:Hexanes to 4:96 EtOAc:Hexanes) yielded the title compound as a colorless oil (30.5 mg, 0.075 mmols, 75% yield) (R/~ 0.45 in 10:90 EtQAciHexanes), enantiomeric excess was found to be 14% by chirai HPLC (Chiralpak OD-H, 1% isopropanol/99% hexane 0.7 mL/min, tr (minor): 13.8 min, tr (major); 18.2 min.; Figure 17, see also Figure 18 for racemic sample) [a]24 D = +27.8° (c 0.78, CH2CI2). 'H MR (400 MHz, CDCI3): The compound exists at a 1.7: 1 mixture of carbamate rotamers. Signals corresponding to the major rotamer: δ 7.27-7.19 (m, 3H), 7.10 (d, J - 7.6 Hz, I H), 6.90 (d, J - 7.6 Hz, 1 H), 5.98 (d, J = 7.6 Hz, 1 H), 5.89-5.81 (m, IH), 4.97-4.76 (m, 3H), 2.67-2.58 (m, 2H), 1.20 (d, J =
6.0 Hz, 3H), 1.16 (d, J = 6.4 Hz, 3 H). Representative signals of the minor rotamer: δ 6.90 (d, J= 7.6 Hz, lH), 6.04 (d, J= 7.6 Hz, lH), 2.77 (dd, J= 14.4, 9.2 Hz, 1H) 1.11 (d, J= 6.4 Hz, 3H). All spectral data matched that previously reported with exception of optical rotation: Literature [<X]24 D for 86% 2,2,2-trichloroethyl (/?)-l-(2-isopropoxy-2- oxoethyl)isoquinoline-2(lH)- carboxylate: -240° (86% ee, c 1.1 , CH2C12).
Results and Discussion
The feasibility of silanediol ion-pair catalysis was studied in the addition of silyl ketene acetal 8 to in situ generated N-acylisoquinoline 6 through proposed ion pair 7 (Table 1). This reaction was selected as a testing ground as it is a process that has documented benefits under the influence of HBD catalysis. Of particular interest were the observations of Taylor and Jacobsen demonstrating thiourea-activation of N-acylisoquinolines (Taylor MS et al., Angew. Chem. Int. Ed. 2005, 44, 6700-6704) and subsequent studies on related systems pointing to thiourea anion binding in the catalytic pathway (Raheem ΓΓ et al., JACS, 2007, 129, 13404-13405; Raheem ΓΓ et al., Org. Lett. 2008, 10, 1577-1580;
Peterson EA, Jacobsen EN, Angew. Chem. Int. Ed. 2009, 48, 6328-6331). Early on, it was found that the solvent played a role in the reaction of 8 with 6 (entries 1-5, Table 1).
Ethereal solvents, such as diethyl ether and methyl terf-butyl ether (MTBE), afforded low yields of product 9 after 40 h with 20 mol % of silanediol 1 (entries 1 and 2).
Dichloromethane gave rise to a good yield of 9 (entry 3); however, the background rate was also high at 88%. Toluene was selected as the solvent to explore in this system as moderate yields of 9 were observed with 20 mol % of silanediol 1 while the background rate remained low at just 12% (entries 4 and 5).
With the solvent identified with achiral silanediol 1, attention was turned to ward the effect of chiral silanediols on catalytic activity for studies on enantioselective catalysis. Catalyst 2, a previously developed chiral C2-symmetric variant of catalyst 1, promoted the reaction i 50% yield (entry 6) (Schafer AG et al., Org. Lett. 2011, 13, 5228-5231).
Concerned that the steric bulk of silanediol 2 was preventing sufficient catalysis, the less sterically encumbered chiral silanediol catalyst 3 was explored. It was found that 20 mol % of silanediol 3 afforded a 75% yield of 9 at -78 °C in toluene (entry 7). The silanediol functionality was determined to affect catalyst activity: dimethoxysilacycle 4 was unable to catalyze the reaction, affording just 14% of 9 (entry 8).
Following the successful catalysis of the addition of silyl ketene acetal 8 to in situ generated N-acylisoquinolinium 7 with racemic silanediol 3, the use of enantiopure silanediols to control the absolute stereochemistry of the acyl Mannich reaction was
investigated. Prior to this study, asymmetric catalysis achieved solely through the HBD activity of a chiral silanediol had not been reported. A factor likely inhibiting advances in asymmetric silanediol catalysis is the difficulty of synthesizing enantioenriched chiral silanediols. Table 1. Silanediol ion-pair catalysis[a]
[a] Reactions performed at a concentration of 0.025 M in the
solvent listed.
[b] Isolated yields
dimethoxysilacycle that readily converts to silanediol (R)-3 upon treatment with
hydrochloric acid in acetone. Scheme 12. Synthesis of enantiopure chiral C2-symmetric silanediol.
The enantiopure silanediol (R)-3 was able to catalyze the addition of silyl ketene acetals to N-acylisoquinolines with promising levels of stereocontrol (Table 2). The silyl group on 8 had a significant effect on the stereochemical outcome: the larger the silyl group the better the enantiomeric excess (entries 1–3). The best enantioselectivity obtained for 9a in this study occurred with the addition of triisopropylsilyl protected 8 to isoquinoline in the presence of 2,2,2-trichloroethyl chloroformate and 1 equiv of (R)-3 (38% ee, entry 4). The absolute stereochemistry of 9a was tentatively assigned (Scheme 13) by analogy to literature precedent (Taylor MS et al., Angew. Chem. Int. Ed. 2005, 44, 6700–6704) (Scheme 14). High yields and encouraging levels of enantiocontrol were also observed with several isoquinolines tested (entries 5–10). For example, 5-bromoisoquinolinium ions were easily incorporated into the process, giving rise to the corresponding products 9b in 57% and 66% yields, with the TIPS and TBS silyl ketene acetals (8) respectively, and up to 26% ee when 20 mol % of (R)-3 was used (entries 5 and 6). 5-Chloroisoquinoline gave rise to 9c in high yield and up to 31% ee with 20 mol % of (R)-3 (entries 7 and 8). Good yields of 9d were isolated (87%) with 50% enantiomeric excess from the incorporation of 5- nitroisoquinoline into the reaction system (entries 9 and 10).
Scheme 13. Tentative stereochemistry based on this work
Scheme 14. Tentative stereochemistry based on Jacobsen’s work (Taylor MS et al., Angew. Chem. Int. Ed. 2005, 44, 6700–6704)
Table 2. Enantioselective ac l Mannich with silanediol R -3.[a]
[a] Reactions performed at a concentration of 0.025 M in toluene.
[b] Isolated yields Evidence supporting a reaction pathway involving silanediol recognition of chloride ions was collected by 1H NMR spectroscopy and X-ray crystallographic analysis. First, 1H NMR spectroscopic analysis found an effect on the OH signals of (R)-3 upon the addition of varying amounts of tetrabutylammonium chloride (TBACl). In the 1H NMR spectrum of pure (R)-3, the OH chemical shift was observed at 2.3 ppm (spectrum (a), Figure 20). As equivalents of TBACl were added to the silanediol, clear downfield shifting of the OH peak (spectra (b)-(f)) was observed. For example, the addition of 5 equiv of TBACl caused the OH chemical shift to be observed at 4.7 ppm, a change of more than 2 ppm (compare spectra (a) vs. (f)). There were also small changes in the chemical shifts observed for the methylene and aromatic hydrogens. Further support of silanediol ion-pair catalysis was
found in the capture of achiral silanediol 1 in a solid-state ion-pair with the hydrochloride salt of isoquinoline (Figure 21).
Conclusions
In summary, silanediols can promote the reaction of silyl ketene acetals with N- acylisoquinolines in good yield, conceivably through anion-binding catalysis. In addition, C2-symmetric silanediols also were shown to exhibit promising levels of enantiocontrol in the title reaction. Example 2:
Introduction
The versatility of the silanediol functionality (Si–(OH)2) continues to grow in organic synthesis. Attractive characteristics of the silanediol functionalities include their hydrogen bonding abilities and their preference to exist as diols, not silanones. The conversion of silanediols into polysiloxanes, polymers with useful properties, is possibly their most well-known function. Albeit less popular, stable silanediols are also accessible and possess their own useful applications. For example, chemists have taken advantage of silanediols to advance new therapeutic agents.
Enantioselective hydrogen bond donor (HBD) organocatalysis is emerging as a powerful tool in complex target construction. Given their hydrogen bonding abilities, silanediols may benefit from improved activities and selectivities versus other HBD catalysts, ultimately enabling unique bond-forming reactions.
Silanediols derived from BINOL-backbones were investigated as catalysts (Scheme 15). There are many advantages of BINOL: it is a readily available, inexpensive source of chirality that is highly customizable in terms of both steric hindrance and electronic nature so as to enable the achievement of optimal reactivity. Scheme 15. BINOL-Based Silanediol Catalyst Designs
2,2'-bis(hexyloxy)- 1 , 1 '-binaphthalene : To a flame-dried 1000 mL round bottom flask was added (R)-BINOL (30.0 g, 105 mmol, ! equiv), n-bromohexane (73.3 mL, 524 mmol, 5 equiv), MeCN (500 mL), and 2CQ3 (72.3 g, 524 mmol, 5 equiv). The flask was equipped with a water-cooled condenser and the reaction was heated to reflux overnight. The reaction was cooled to 23°C, di luted with H2O, and extracted with hexanes (3x). The combined organic layers were dried with Na2S04, concentrated in vacuo, and distilled to remove excess n-bromohexane (120°C, -300 mTorr) to provide the title compound as colorless viscous oil (46.7 g, 103 mmol, 98%; contains ~5% residual /t-bromohexane), Ή NMR (400 MHz, CDCI3) δ 7.96 (d, ./ 9.0 Hz, 2H), 7.89 id. J 8.1 Hz, 21 1 K 7.45 (d, 9.0 Hz, 2H), 7.34 (ddd, J = 1 .9 Hz, 6.1 Hz, 8.0 Hz, 21 1 ). 7.20-7.23 (4H), 3.97 (4H), 1 .40- 1.44 (4H), 0.95-1.10 (12H), 0.79 ft, J= 7.1 , 6H). Ail other spectra data matched that previously reported (Gong Z et al. J. Org. Chem. 2001 , 66, 2358-2367).
4,4,.6,6'-fetrabromo-2.2'-bis(hexyloxy)-l , 1 '-binaphthalene: To a flamed-dried 500 mL round bottom flask was added 2,2'-bis(hexyloxy)-l ,r-binaphthalene (16.9 g, 37.1 mmol, equiv) followed by AcOH (300 mL). Bromine (20.1 mL, 390.5 mmol, 10.5 equiv) was added slowly to the solution at 23°C and the reaction was stirred for 4,5 h at 23°C. The reaction was cooled to 0°C, quenched with saturated NaHSC , and extracted with CH2CI2 (3x). The combined organic layers were washed with NaHCOs, then brine, dried with Na2S04, and concentrated in vacuo. The compound was purified via flash column chromatography (dry load) on silica gel (100% hexanes) to provide the title compound as a light yellow- oil (18.2 g, 23.6 mmol, 64%). R/= 0.65 (10:90 ethyl acetate:hexanes), ιΆ NMR (400 MHz, CDCI3) δ 8.39 (d, J= 1.9 Hz, 2H), 7.71 (s, 2H), 7.31 (dd, J = 2.0, 9.1 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 3.92 (4H), 1.37-1.44 (4H), 0.88-1.12 (12H), 0.76 (t, J= 7.1 Hz, 6H); 13C NMR (100 MHz, CDCI3) δ 154.5, 133.2, 130.7, 129.5, 128.9, 127.4, 122.5, 120.5, 1 19.3, 69.9, 31.3, 29.2, 25.4, 22.6, 14.0. All other spectra data matched that previously reported (Gong Z et al. J. Org. Chem. 2001, 66, 2358-2367).
4,4',6,6' tetrabromo-[ 1 , 1 '-binaphthalene]-2,2'-diol (R)-26 : Adapting a procedure by Lin (Mi L et al. JACS 2009, 131, 4610-4613), to a flame-dried 250 mL round bottom flask was added 4,4',6,6,-tetrabromo-2,2,-bis(hexyloxy)- 1 , 1 '-binaphthalene (20.9 g, 27.1 mmol, 1 equiv) followed by CH2CI2 (60 mL). The solution was cooled to -78°C and BBra (2.26 mL, 23.8 mmol, 6 equiv) was added dropwise. The reaction was warmed to 23°C and stirred overnight. The reaction was cooled to 0°C, quenched with water (-20 mL), and extracted with CH2CI2 (3x). The organic layers were combined, washed with brine, dried with
Na2.S0 , and concentrated in vacuo. The resulting compound was purified via silica plug (CH2CI2) to afford (R)-26 as a white solid (16.1 g, 26.7 mmol, 99%). R/= 0.56 (30:70 ethyl acetate:hexanes), \ R (400 MHz, CDCI3) δ 8.46 (d. J ------ 1.9 Hz, 2H), 7.75 (s, 2H), 7.43
(dd, ,/ 1.9 Hz, 8.9, 2H), 6.96 (d, J= 8.9 Hz, 2H), 4.95 (s, 21 ! }. i C NMR (100 MHz, CDC13) 6 152.7, 132.5, 132.1, 130.3, 129.6, 126.3, 125.1, 123.2, 120.1, 110.4; m.p. 293- 294°C; IR ( aCl) 3500, 3080, 2916, 1580, 1493, 1373, 1176, 937, 733 cm'1; HRMS (ESI): Mass calculated for C2oH10Br402Na [M+Naf, 620.7307. Found [M+Naj+, 620.7300; [a]23 D = - 9.8° (c 1.00, CHCh).
4,4',6,6'-tetraphenyl-[ 1 , 1 '-binaphthalene]-2,2'-diol: To a 150 mL flame-dried round bottom flask was added (i?)~26 (6.66 g, 11.1 mmol, 1 equiv), phenylboronic acid (5.94 g, 48.7 mmol, 4.4 equiv), K2CO3 (9.17 g, 66.4 mmol, 6 equiv), THE (35 mL), Pd(PPh3)4 (1.92 g, 1.66 mmol, 0.15 equiv) and H20 (33 mL). The flask was equipped with a water-cooled condenser and the reaction was heated to reflux overnight. The reaction was cooled to 23°C and extracted with CH2CI2 (3x). The combined organic layers were washed with brine, dried with Na2.S()4, and concentrated in vacuo. The resulting residue was first subjected to flash column chromatography on silica gel (100% CH2CI2) to remove the black colored impurity followed by additional purification via flash column chromatography on silica gel (30:70 CH2Cl2:hexanes to 100% CH2CI2) to provide the title compound as an off-white solid (4.03 g, 6.82 mmol, 62%). R. 0.46 (30:70 ethyl acetate: he anes); "Ή NMR (400 MHz, CDCI3) δ 8.18 (br d, J = 8.2 Hz, 2H), 7.49-7.69 (16H), 7.39-7.47 (8H), 7.30-7.34
(2H), 5.20 (s, 2H); 13C NMR (100 MHz, CDCI3) δ 152.5, 144.4, 141.2, 140.0, 137.1, 133.3, 130.1, 129.0, 128.7, 128.4, 128.0, 127.4, 127.33, 127.27, 125.4, 125.0, 119.3, 110.5; [aj , D
-49.8° (c Q.26, CHC13) All other spectra data matched that previously reported (Gong Z et al. J. Org. Chem. 2001, 66, 2358-2367).
4,4',6,6'-tetraphenyl-[ 1 , 1 '-binaphthalene]-2,2'-diyl bisftrifluoromethanesulfonate)
(Hashimoto T et al. Tetrahedron: Aymmetry 2003. 14, 1599-1602): To a 150 mL flame- dried round bottom flask was added 4,4',6,6'-tetraphenyl-[ 1 , 1 '-binaph.thalene]-2,2'-diol (5.13 g, 8.68 mmol, 1 equiv) followed by CH2CI2 (50 mL). The solution was cooled to -78°C and Et3N (3.60 mL, 26.04 mmol, 3 equiv) was added followed by the addition of TfiO (4.37 mL, 26.04 mmol, 3 equiv) dropwise. The reaction was wanned to 23°C and stirred overnight. The reaction was cooled to 0°C, quenched with 2 M HC1 (~10 mL), and extracted with CH2CI2 (3x). The combmed organic layers were washed with NaHCOs, brine, dried with a2S04, and concentrated in vacuo. The resulting compound was run through a silica gel plug (CH2CI2 as eluent) and then purified via flash column
chromatography on silica gel (100% hexanes to 5:95 Et20:hexanes) to provide the title compound as a white solid (6.21 g, 7.26 mmol, 84%). R/= 0.35 (10:90 ethyl
acetate:hexanes); m.p. 205-207°C; lU NMR (400 MHz, CDCb) δ 8.25 (br d J ------ 1.6 Hz,
2H), 7.54-7.74 (20H), 7.41-7.45 (4H), 7.34-7.38 (2H), i3C NMR (100 MHz, CDCb) δ 145.2, 145.0, 140.4, 140.2, 138.9, 133.1, 131.4, 130.2, 129.1, 128.9, 128.6, 128.1, 128.0, 127.7, 127.6, 124.6, 122.7, 120.7, 1 18.4 (q, JCF = 320 Hz); m.p. 205-207°C; 1R (Nad) 3058, 3028, 1560, 1486, 1419, 1210, 1136, 942 cm ; HRMS (ESI): Mass calculated for
[M+Na]+, 877.1 124. Found [M+Na]+, 877.1 1 12; [o|23 D = -67.3° (c 1 .00, CHCb).
2,2'~dimethyl -4,4',6,6'~tetrapheny 1- 1 , Γ-binaph thalene (R}~27 (Hashimoto T et al.
Tetrahedron: Aymmetry 2003, 14, 1 99-1602): To a 150 mL flame-dried round bottom flask was added 4,4',6,6'-tetxaphenyl-[i, r-binaphthaiene]-2,2'-diyl bis(trifluoromethanesulfonate) (6.21 g, 7.26 mmol, 1 equiv), Et20 (65 mL), and Ni(dppp)Cl2 (197 mg, 0.363 mmol, 0.05 equiv). The mixture was cooled to 0°C and 2.44 M MeMgBr (13.7 mL, 33.4 mmol, 4.6 equiv) was added drop wise. The flask was equipped with a water-cooled condenser and the reaction was heated to reflux overnight. The reaction was cooled to 23°C and slowly poured in a chi lled flask of 2 M HC1 (-25 mL). The mixture was filtered through celite and extracted with Et20 (3x). The combined organic layers were washed with NaHCC , brine, dried with 'Na2S04, and concentrated in vacuo. The resulting compound was purified with flash column chromatography on silica gel (5:95 Et20:hexanes to 10:90 Et20:hexanes) to afford (R)-27 as a white solid (3.88 g, 6.61 mmol, 91%), R . 0.43 (10:90 ethyl
acetate :hexanes); lB NMR (400 MHz, CDCb) δ 8.20 (br d, J= 1.7 Hz, 2H), 7.68-7.71 (4H), 7.46-7.59 (14H), 7.28-7.42 (8H), 2.18 (s, 6H); 13C NMR (100 MHz, CDCb) δ 141.5, 141.0, 140.2, 137.8, 134.8, 134.3, 132.6, 130.8, 130.6, 130.4, 128.9, 128.6, 127.51 , 127.47, 127.3, 126.9, 125.8, 124.3, 20.4; m.p. 198-201°C; IR (NaCl) 3056, 3029, 2917, 1598, 1471, 1449, 1382 cm"1; HRMS (ESI): Mass calculated for C u- b iXa [ Na j . 609.2553. Found [M+Naf, 609.2538; [a]23 D = -89.0° (c 0.200, CHCb).
I .7.9. i 4-;eiraphcnyi-3,5-dihydro-4l bdnu^lnhoj 2. 1 -c : 1 *.2'-c hiiepinc-4,4-diui
22b: Adapting a procedure by Mattson (Schafer AG et al. Angew. Chem. Int. Ed. 2013, 52, 11321-1 1324), to a 250 mL flame-dried round bottom flask was added (R)-27 (4.51 g, 7.69 mmol, 1 equiv) followed by Et20 (70 mL). The solution was cooled to 0°C and 1.6 M n- BuLi (14.4 mL, 23.07 mmol, 3 equiv) was added dropwise followed by the addition of TMEDA (3.44 mL, 23.07 mmol, 3 equiv) dropwise. The reaction was warmed to 23°C and stirred overnight. The reaction was then cooled to 0°C and Si(OMe)4 (4.55 ml, 30.8 mmol,
4 equiv) was added drop-wise followed by Et2Q (35 mL). The reaction was warmed to 23°C and stirred for 24 h. The mixture was pushed through a pad of silica gel using Et20 as the el ent. After concentration in vacuo, the compound was partially purified via flash column chromatography on silica gel (100% hexanes to 80:20 hexanes:Et20) to afford slightly impure (i?)-25b (2.88 g), which was carried on to the next hydrolysis step. To a flame dried 1000 mL flame-dried round bottom flask was added crude (/?)-25b (2.88 g) and acetone (300 mL). The solution was cooled to 0°C followed by the dropwise addition of 1 M HCl (75 mL). The mixture was stirred at 0°C for 6 h. The reaction was diluted with Et2() (-150 mL), neutralized to pH 7 using NaHCC , and extracted with Et20 (3x). The organic layers were combined, dried with Na2S04 and concentrated in vacuo. Evaporation under high vacuum was necessary to remove a volatile white liquid before purification. The resulting compound was purified via flash column chromatography on silica gel (40:60 Et20:hexanes to 80:20 Et20:hexanes) to afford a white solid (R)-22b (1.46 g, 2.17 mmol, 28% over 2 steps) as a 3: 1 Et20 complex. R. 0.42 (50:50 ethyl acetate:hexanes); ' ! ! NMR (400 MHz, CDCb) δ 8.22 (br d, J= 1.7 2H), 7.68-7.70 (4H), 7.46-7.58 (14H), 7.38-7.42 (6H), 7.29- 7.33 (2H), 2.43 (s, 2H), 2.31 (d, J= 13.7 Hz, 2H), 2.25 (d, 13.7, J= 13.7 Hz, 2H); 13C NMR (100 MHz, CDCb) δ 141 .2, 140.9, 140.6, 137.3, 134.3, 132.4, 132.2, 130.4, 130.3, 129.5, 128.8, 128.4, 127.6, 127.4, 127.3, 127.1, 125.6, 124.1, 23.5; m.p. 344-346 °C; IR (KBr) 3416, 3051 , 3021, 2954, 2917, 1628, 1590, 1561, 1486, 1158, 1 143, 830, 756, 696 cm"1; HRMS (ESI): Mass calculated for C46H3402SiNa [M+Na]+, 669.2220. Found [M+Na] , 669.2207; [CC]23D - -201° (c 1.00, CHCb).
General procedure for N-acyl Mannich Reaction: An 8 mL vial was equipped with a magnetic stir bar and screw cap was sealed with a virgin septum, flame dried under vacuum, purged with N2, and then placed under a positive pressure of argon. A 0.10 M stock solution of the appropriate freshly purified isoquinoiine was prepared in toluene which had been passed through a bed of active alumina and freshly distil led from CaH2. isoquinoiine solution (1.0 mL, 0.10 mmol, 1.0 equiv) was transferred to the reaction vial and placed in an ice bath, A 0.1 1 M stock solution of the appropriate chloroformate was prepared in toluene. Chloroformate solution (1.0 mL, 0.11 mmol, 1.1 equiv) was added drop-wise to the cold isoquinoiine solution, the ice bath was removed and the reaction mixture wanned to r.t over 30 min. The reaction mixture was diluted with toluene (1.50 mL). A 0.020 M solution of catalyst (j?)~22b was prepared in toluene. The reaction mixture was cooled in a dry ice acetone bath, and the catalyst (j?)-22b solution (1.0 mL, 0.020 mmols, 0.20 equiv) was added to the reaction mixture and stirred for 5 mins. A 0.30 M solution of the appropriate
silyl ketene acetal was prepared in toluene, and was added (0.50 mL, 0.15 mmols, 1.5 equiv) drop-wise to the reaction mixture, which was immediately transferred to a–55°C acetone bath equipped with immersion cooling coil or a–35°C freezer. The reaction stirred for either 6 or 14 h, after which it was quenched by the addition of NaOMe (0.20 mL of 0.5 M in MeOH). The reaction mixture was filtered through a silica gel plug using ethyl acetate as the eluent, and solvent was removed in vacuo. The product was isolated via flash column chromatography on silica gel using the conditions detailed in the supporting information. Further purification through an activity II alumina plug with minimal dichloromethane (~2 mL) as the eluent yielded the pure product. Enantiomeric ratios were determined by HPLC analysis under the conditions detailed in the supporting information. BINOL-Based Silanediol Synthesis
Studies herein began with the synthesis of 5-membered silacycles 21 (Scheme 16). Following literature protocols (Takaya H et al., Org. Syn. 1989, 67, 20–32), 23a (R = H) was readily converted to 24a. Silacyclization of 24a attempted under numerous conditions met with no success. It was reasoned that the difficult preparation of 21a might lie in its low stability, plausibly due to the location of the silicon in the highly strained 5-membered ring. It was hypothesized that silanediol 21b, with phenyl substituents in the 3,3’-positions stabilizing the silacycle, would be more synthetically accessible. Indeed, silanediol 21b was prepared in four steps from BINOL. The silacyclization protocol was found to be lithiation with n-BuLi followed by reaction with silicon tetrachloride then aqueous workup. The structure of 21b was confirmed by small molecule X-ray crystallographic analysis (Figure 22).
Given the possible limitations of 5-membered silacycles 21, efforts were redirected to 7-membered silacyclic silanediols 22 derived from (R)-2,2’-binaphthlene (e.g., (R)- BINOL). The advantage of this scaffold is that the chirality of the BINOL starting material is retained over the course of the synthetic sequence enabling direct access to enantiopure silanediols, meaning issues with enantioerosion due to unstable intermediates are avoided. Starting from (R)-BINOL, a straightforward four-step protocol was established, detailed in Scheme 17. (R)-BINOL is treated with Tf2O, followed by nickel-catalyzed Kumada cross- coupling with MeMgBr to provide (R)-2,2’-dimethyl-1,1’-binaphthlene. Deprotonation of both benzylic methyl groups with n-BuLi/TMEDA, followed by quenching with Si(OMe)4, affords dimethoxysilacycle (R)-25. Simple hydrolysis with dilute HCl gives silanediol (R)- 22. After neutralization with sodium bicarbonate, dissolution and concentration from anhydrous Et2O, the silane diol 22 was obtained as a 2:1 complex with diethyl ether.
Silanediol (R)-22-Et2O is an air and moisture stable white solid at room temperature that can be stored on the benchtop for several weeks. Attempts at removing the ethereal solvent of complexation led to rapid decomposition of the silanediol. Using this procedure, enantiopure (R)-22 can be produced on a multi gram scale. (The structure of bis-TMS protected (R)-22 was confirmed by X-ray crystallographic analysis (Figure 23).
Scheme 18 outlines the general route to the 4,4’,6,6’-tetrasubstituted catalysts.
Drawing from the established protocols (Hu QS et al., J. Org. Chem. 1999, 64, 7528–7536), (R)-BINOL is bis-O-hexylated, followed by four-fold bromination and dealkylation with BBr3 to provide (R)-26. A Suzuki-Miyaura cross-coupling with PhB(OH)2 provided the phenyl substituents. Subsequent triflation of the free alcohols in the 2,2’ positions enabled a nickel-catalyzed Kumada cross-coupling with MeMgBr provides access to the (R)-27, the precursor to silacyclization. Deprotonation of the 2,2’ methyl groups, affected with n-BuLi and TMEDA, was followed with the addition of excess Si(OMe)4 to give the
dimethoxysilacycle (R)-25b. Simple hydrolysis of (R)-25b with aqueous HCl followed by treatment with diethyl ether and neutralization then afforded silanediol (R)-22b as a 3:1 complex with Et2O. Attempts to confirm the structure of (R)-22b in the solid state led to the formation of a siloxane trimer (Figure 24). Scheme 18. Synthesis of 4,4',6,6'-tetraphenyl substituted silanediol (R)-22b.
Ph
intermediate (R)-28. The deprotection and triflation of the 2,2’ hydroxyl groups allowed for their conversion to the requisite methyl group via a nickel-catalyzed cross coupling. The silacyclization of (R)-29 occurred under standard reaction conditions to afford
dimethoxysilacycle (R)-25c. Hydrolysis of (R)-25c was achieved under standard conditions and (R)-22c was isolated as a 2:1 complex with Et2O. Scheme 19. Synthesis of 6,6'-diphenyl substituted silanediol (R)-22c.
Catalysis with BINOL-Derived Silanediols
With a small family of BINOL-based silanediols in hand, the effect of catalyst structure on activity and stereoselectivity in the addition of silyl ketene acetals to N-acyl isoquinolinium ions was studied. This N-acyl Mannich reaction was selected as the platform for the structure activity relationship studies as it has been found that silanediols can effect this transformation, possibly via anion-binding catalysis (Schafer AG et al. Angew. Chem. Int. Ed. 2013, 52, 11321-11324). In general, enantioselective anion-binding catalysis is a relatively new mode of action for HBD catalysts, and previously only ureas and related thioureas had been shown to act as catalysts in this fashion (Brak K et al. Angew. Chem. Int. Ed. 2013, 52, 534-561).
This N-acyl Mannich reaction system presented a platform for studying the effect of substitution patterns on the catalytic ability of the silacyclic catalyst (Table 3). The initial finding with unsubstituted silanediol (R)-22a gave rise to 33a in 62% yield in an
enantiomeric ratio of 61:39. Silanediol (R)-22c with phenyl rings solely in the 6,6’ positions
afforded little improvement over this result, leading to 33a in 65% yield and 20% enantiomeric excess. On the other hand, adding phenyl rings in the 4,4’ positions provided a significant increase in enantiomeric enrichment. Specifically, catalyst (R)-22d gave rise to 57% of 33a with a 10% improvement in enantiomeric excess over catalyst (R)-22a. Adding substitution at the 4,4’ and 6,6’ positions, e.g. silane diol (R)-22b, afforded 33a in good yield with the best enantiomeric ratio (72:28 e.r.). It was impressive that the addition of four phenyl rings to the 4, 4’, 6, 6’ positions of the silane diol scaffold was able to more than double enantiomeric excess compared to substitution only at the 6,6’ position as in catalyst (R)-22c. Table 3. Influence of Silanediol Backbone on Enantioselectivit .
A reaction temperature of -55°C was identified as optimal for both yield and enantioselectivity (entries 5-8 of Table 5). At -45°C, 33a was isolated in 55% yield with an
enantiomeric ratio of 78:22 under the influence of 20 mol% 22b (entry 6 in Table 5). At a catalyst loading of 50 mol%, 33a was isolated in nearly 80% ee at -78°C in 0.005 M toluene, although the yield was just 39% after 120 hours (entry 8 in Table 5). Table 5. Optimization of N-acyl Mannich reaction.
Scheme 21. Comparison of silane diol catalysts (R)-22a to (R)-22b under optimized reaction conditions.
Table 6. Substrate scope of N-acyl Mannich reaction.
20 mol-%
Silyl Ketene Acetal:
In order to gain more insight into the salient structural and mechanistic aspects of these catalysts, absolute values for the pKas and the binding constants with a variety of anions, both of which have been shown to be important properties in HBD organocatalysis reactivity and selectivity (Li X et al., Chem.–Eur. J. 2010, 16, 450–455), were studied. The Brodwell method has previously been used to determine the pKas of several urea-based
hydrogen bond donors (Jakab G et al. Org. Lett. 2012, 14, 1724-1727), the same approach was used to find the pKas of achiral di(naphthalen-1-yl)silanediol 34, (R)-22a, and (R)-22b (Figure 25). The pKa values of these three representative silanediols were all ~19 in DMSO. This is in the same range as Jacobsen’s chiral thiourea, a catalyst able to induce similar enantioselective N-acyl Mannich reactions (Taylor MS et al. Angew. Chem. Int. Ed. 2005, 41, 6700-6704; Jakab G et al. Org. Lett. 2012, 14, 1724-1727). Since both reactivity and selectivity are associated with a low pKa of the HBD catalyst, the fact that the pKa of all three silanediols tested was ~19 might indicate a lack of tunability within the catalyst structure. However, despite similarities in pKa, the differences in enantioselectivity of N- acyl Mannich observed between the (R)-22a and (R)-22b catalysts suggests that factors outside of acidity can influence the ability of silane diols to impart sterocontrol over N-acyl Mannich reactions.
The binding affinities for the same silanediols above (e.g., (R)-22a and (R)-22b) with chloride in CDCl3 were also determined. Kondo has previously reported the binding constant between chloride and achiral di(naphthalen-1-yl)silanediol 34 to be 1.44 ± 0.11 × 102 molΫ1 dm3 (Figure 25) (Kondo S et al., Org. Lett. 2006, 8, 4621–4624). The binding constant for (R)-22a and (R)-22b were determined using the same approach as reported by Kondo et al. (Kondo S et al., Org. Lett. 2006, 8, 4621–4624): a 1H NMR titration of the silanediols with tetrabutylammonium chloride was conducted and the change in chemical shift of the O-H protons was measured. From this data, the binding constant of (R)-22a and (R)-22b were determined to be 2.19 ± 0.03 × 102 MΫ1 and 3.10 ± 0.10 × 102 M-1, respectively (Figure 25).
Figure 26 illustrates the 1H NMR titration of (R)-22b with tetrabutylammonium chloride. The binding stoichiometry was determined to be 1:1 silanediol:chloride as can be seen from the maximum at ~ 0.5 in the Job's plot (Figure 27).
Solid state data regarding the silanediols bound with both anions alone (Kondo S et al. Org. Lett. 2006, 8, 4621-4624) and with isoquinolinium ion pairs also support their anion-binding mode of action and offers insight into potential non-covalent interactions supporting the transition state of the major reaction pathway. The crystal structure of the bis TMS ether (R)-22a is shown in Figure 23. Additionally, a single crystal of an ion pair composed of di(naphthalen-1-yl)silanediol 34 and the HCl salt of isoquinoline was obtained (Figure 28) (Schafer AG et al. Angew. Chem. Int. Ed. 2013, 52, 11321-11324).
All of the evidence taken together strongly suggests an anion-binding mode of catalysis (Figure 29). The proposed reaction pathway begins with in situ formation of the
acyl isoquinoline (A). The silane diol catalyst is then able to encourage formation of the isoquinolinium ion-pair B through hydrogen bonding to the chloride. Formation of the carbon-carbon bond occurs upon reaction of B with the silyl ketene acetal to yield ion pair C. The desilylation of the oxocarbenium ion with chloride then generates the product and frees the silanediol to initiate another reaction.
Conclusions
To conclude, a class of anion-binding organocatalysts that efficiently catalyze enantioselective N-acyl Mannich reactions was developed. These modifiable silanediols are readily prepared in enantiopure form and are bench stable indefinitely. The studies herein further suggest a network of noncovalent interactions such as - ǡ -cation, hydrogen bonding and electrostatic forces can contribute to the stabilization of the transition state leading to the major enantiomer.
Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims
1. A compound defined by Formula I:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R4, R5, R6, R2’, R3’, R4’, R5’, and R6’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, R3 and R4, R4 and R5, R5 and R6, R2’ and R3’, R3’ and R4’, R4’ and R5’, R5’ and R6’, or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
R7 and R7’ are each independently chosen from H, OH, and halogen;
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy,
substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
or wherein, as valence and stability permit, R8 and R9, together with the atoms to which they are attached, form a 7-9 membered silacycle;
with the proviso that when R8 and R9, together with the atoms to which they are attached, form a 7-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both phenyl.
2. The compound of claim 1, wherein when R8 and R9, together with the atoms to
which they are attached, form a 9-membered silacycle, R1, R1’, R2-R7 and R2’-R7’ are not all H.
3. The compound of claim 1 or 2, wherein when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1 and R1’ are not both -CH3; and R2-R7 and R2’-R7’ are not all H.
4. The compound of any of claims 1-3, wherein when R8 and R9, together with the atoms to which they are attached, form a 9-membered silacycle, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from the moieties shown below.
5. The compound of any of claims 1-4, wherein R1 and R1’ are chosen from hydrogen and–CH3.
6. The compound of any of claims 1-5, wherein R1 and R1’ are both hydrogen.
7. The compound of any of claims 1-6, wherein R2 and R2’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
8. The compound of any of claims 1-7, wherein R2 and R2’ are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an
electron withdrawing group, and
p is chosen from 1, 2, 3, 4 and 5.
9. The compound of any of claims 1-8, wherein R3 and R3’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
10. The compound of any of claims 1-9, wherein R3 and R3’ are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an
electron withdrawing group, and
p is chosen from 1, 2, 3, 4 and 5.
11. The compound of any of claims 1-10, wherein R4 and R4’ are independently chosen from hydrogen, hydroxy, and halogen.
12. The compound of any of claims 1-11, wherein R5 and R5’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
13. The compound of any of claims 1-12, wherein R5 and R5’ are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an
electron withdrawing group, and
p is chosen from 1, 2, 3, 4 and 5.
14. The compound of any of claims 1-13, wherein R6 and R6’ are independently chosen from hydrogen, hydroxy, and halogen.
15. The compound of any of claims 1-14, wherein R7 and R7’ are both hydrogen.
16. The compound of any of claims 1-15, wherein R8 and R9 are individually chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
17. The compound of any of claims 1-16, wherein R8 and R9 are independently chosen from the moieties shown below
electron withdrawing group, and
p is chosen from 1, 2, 3, 4 and 5.
18. The compound of any of claims 8-17, wherein the electron donating group is
selected from hydroxy, substituted or unsubstituted amino, substituted or unsubstituted amido, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryl.
19. The compound of any of claims 8-18, wherein the electron withdrawing group is selected from nitro, cyano, and trihalides.
20. The compound of any of claims 1-19, wherein the compound is defined by Formula II
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R4, R5, R6, R2’, R3’, R4’, R5’, and R6’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, R3 and R4, R4 and R5, R5 and R6, R2’ and R3’, R3’ and R4’, R4’ and R5’, or R5’ and R6’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R7 and R7’ are each independently chosen from H, OH, and halogen;
with the proviso that when n=0 and m=0, R1, R1’, R3-R7 and R3’-R7’ are not all H and R2 and R2’ are not both phenyl.
21. The compound of claim 20, wherein when n is 1 and m is 1, R1, R1’, R2-R7 and R2’- R7’ are not all H.
22. The compound of claim 20 or 21, wherein when n is 1 and m is 1, R1 and R1’ are both–CH3; and R2-R7 and R2’-R7’ are not all H.
23. The compound of any of claims 20-22, wherein when n is 1 and m is 1, R1, R1’, R3- R7 and R3’-R7’ are not all H and R2 and R2’ are not both chosen from the moieties below:
24. The compound of any of claims 20-23, wherein n is 1 and m is 1.
25. The compound of any of claims 20-24, wherein the compound is defined by Formula III:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R2 and R3, and/or R2’ and R3’, together with the atoms to which they are attached, form a 3- 10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms;
with the proviso that when n=0 and m=0, R1, R1’, R3, R5, R3’, and R5’ are not all H, and R2 and R2’ are not both phenyl.
26. The compound of claim 25, wherein the compound is defined by Formula IIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R2 and R3, and/or R2’ and R3’ together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms.
27. The compound of any of claims 20-25, wherein the compound is defined by
Formula IV:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen,
hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
28. The compound of claim 27, wherein the compound is defined by Formula IVa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen,
hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or
unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
29. The compound of claim 27 or 28, wherein the compound is defined by the formula:
30. The compound of claim 27 or 28, wherein the compound is defined by the formula:
31. The compound of any of claims 20-26, wherein the compound is defined by
Formula V:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
32. The compound of claim 31, wherein the compound is defined by Formula Va:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
33. The compound of claim 31 or 32, wherein the compound is defined the formula:
.
34. The compound of claim 31 or 32, wherein the compound is defined by the formula:
35. The compound of any of claims 20-26, wherein the compound is defined by
Formula VI:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted
or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl..
36. The compound of claim 35, wherein the compound is defined by Formula VIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
37. The compound of claim 35 or 36, wherein compound is defined be the formula:
38. The compound of claim 35 or 36, wherein the compound is defined be the formula:
39. The compound of any of claims 20-26, wherein the compound is defined by
Formula VII:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl;
with the proviso that when n=0 and m=0, R1 and R1’ are both H and R2 and R2’ are not both phenyl.
40. The compound of claim 39, wherein the compound is defined by Formula VIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
41. The compound of any of claims 20-26, wherein the compound is defined by
Formula VIII:
wherein
n = 0 or 1;
m = 0 or 1; and
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl.
42. The compound of claim 41, wherein the compound is defined by Formula VIIIa:
wherein
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl.
43. The compound of claim 41 or 42, wherein the compound is defined by the formula:
44. The compound of claim 41 or 42, wherein the compound is defined by the formula:
45. The compound of any of claims 20-44, wherein the compound is a complex with diethyl ether.
46. The compound of claim 45, wherein the compound is a 2:1 complex with diethyl ether.
47. The compound of any of claims 1-19, wherein the compound is defined by Formula IX:
R5'
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2, R3, R5, R2’, R3’, and R5’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit,
independently R2 and R3
, R2’ and R3’, or R2’ and R9, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
48. The compound of any of claims 1-19, wherein the compound is defined by Formula X:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3, R5, R3’, and R5’ are each independently chosen from hydrogen, halogen,
hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
49. The compound of any of claims 1-19, wherein the compound is defined by Formula XI:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R3 and R3’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl,
substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
50. The compound of any claims 1-19, wherein the compound is defined by Formula XII:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R5 and R5’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
51. The compound of any of claims 1-19, wherein the compound is defined by Formula XIII:
wherein
n = 0 or 1;
m = 0 or 1;
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R2 and R2’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
52. The compound of any of claims 1-19, wherein the compound is defined by Formula XIV:
wherein
n = 0 or 1;
m = 0 or 1; and
R1 and R1’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl; and
R8 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and
R9 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
53. The compound of any of claims 48-52, wherein m is 0 and R9 is substituted or unsubstituted aryl.
54. The compound of any of claims 48-53, wherein R8 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5
55. The compound of any of claims 48-54, wherein the compound is
56. A compound defined by Formula XV:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R11, R12, R13, R14, R15, R16, R17, R12’, R13’, R14’, R15’, R16’, and R17’ are each
independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R11 and R12, R12 and R13, R13 and R14, R14 and R15, R15 and R16, R16 and R17, R12’ and R13’, R13’ and R14’, R14’ and R15’, R15’ and R16’, or R16’ and R17’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl,
substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
57. The compound of claim 56, wherein R10 and R10’ are chosen from hydrogen and -CH3.
58. The compound of any of claims 56 or 57, wherein R11 is selected from hydrogen, hydroxy, and halogen.
59. The compound of any of claims 56-58, wherein R12 and R12’ are independently chosen from hydrogen, hydroxy, and halogen.
60. The compound of any of claims 56-59, wherein R13 and R13’ are independently chosen from hydrogen, hydroxy, and halogen.
61. The compound of any of claims 56-58, wherein R12 and R13 together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms.
62. The compound of claim 61, wherein R12 and R13 together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
63. The compound of any of claims 56-58 or 59-60, wherein R12’ and R13’ together with the atoms to which they are attached, form a 5-7 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms.
64. The compound of claim 63, wherein R12’ and R13’ together with the atoms to which they are attached, form a substituted or unsubstituted phenyl moiety.
65. The compound of any of claims 56-64, wherein R14 and R14’ are independently chosen from hydrogen, hydroxy, and halogen.
66. The compound of any of claims 56-65, wherein R15 and R15’ are independently chosen from hydrogen, hydroxy, and halogen.
67. The compound of any of claims 56-66, wherein R16 and R16’ are independently chosen from hydrogen, hydroxy, and halogen.
68. The compound of any of claims 56-67, wherein R17 and R17’ are individually chosen from hydrogen, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
69. The compound of any of claims 56-68, wherein R17 and R17’ are independently chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an
electron withdrawing group, and
p is chosen from 1, 2, 3, 4 and 5.
70. The compound of any of claims 56-69, wherein R18 is chosen from substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
71. The compound of any of claims 56-70, wherein R18 is chosen from the moieties shown below
wherein EDG represents an electron donating group and EWG represents an
electron withdrawing group, and p is chosen from 1, 2, 3, 4 and 5.
72. The compound of any of claims 56-71, wherein the compound is defined by
Formula XVa:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R12, R13, R17, R12’, R13’, and R17’ are each independently chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, independently R12 and R13, or R12’ and R13’, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
73. The compound of claim 72, wherein the compound is defined by Formula XVb:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R17 and R17’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
74. The compound of claim 73, wherein the compound is defined by the formula:
75. The compound of claim 72, wherein the compound is defined by Formula XVc:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R12, R13, R17, and R17’ are each independently chosen from hydrogen, halogen,
hydroxy, substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted
alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl, or wherein, as valence and stability permit, R12 and R13, together with the atoms to which they are attached, form a 3-10 membered substituted or unsubstituted cyclic moiety optionally including between 1 and 3 heteroatoms; and
R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
76. The compound of claim 75, wherein the compound is defined by Formula XVd:
wherein
n = 0 or 1;
R10 and R10’ are each independently chosen from H and substituted or unsubstituted C1-C4 alkyl;
R17 and R17’ are each independently chosen from hydrogen, halogen, hydroxy,
substituted or unsubstituted amino, silyl, thiol, substituted or unsubstituted thioalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl; and R18 is chosen from hydrogen, halogen, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
alkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkylheterocycloalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl, substituted or unsubstituted alkylheteroaryl, or substituted or unsubstituted heteroaryl.
77. A catalytic composition comprising a compound defined by any of claims 1-76.
78. A method of performing a reaction selected from
(a) a nucleophilic conjugate addition reaction, in which a first organic species
comprising a nitroalkene reacts with a second organic species comprising a nucleophile to provide a product; or
(b) an acyl Mannich type reaction in which a first organic species comprising an amine reacts with a second organic species comprising a carbonyl containing compound to provide a product;
(c) an epoxide ring opening reaction, in which a first organic species comprising an epoxide reacts with a second organic species comprising a nucelophile to provide a product;
(d) a sequestration of carbon dioxide reaction, in which a first organic species comprising carbon dioxide reacts with a second organic species comprising a reservoir to provide a product;
the method comprising contacting the first organic species and the second organic species with a catalytically effective amount of a compound defined by any of claims 1-76 or the catalyst composition defined by claim 77 under conditions effective to form the product.
79. A method of detecting an analyte comprising contacting the analyte with a
compound defined by any of claims 1-76, and evaluating an optical property of the compound to detect, identify, or quantify the analyte.
80. The method of claim 79, wherein the optical property of the compound comprises luminescence.
81. The method of claim 79 or 80, wherein the luminescence comprises fluorescence.
82. The method of any of claims 79-81, wherein the optical property includes a change in the fluorescence of the compound upon contacting the analyte.
83. The method of any of claims 79-82, wherein the analyte comprises a chiral
compound.
84. The method of any of claims 79-83, wherein the analyte comprises an anion.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360938A (en) * | 1991-08-21 | 1994-11-01 | Union Carbide Chemicals & Plastics Technology Corporation | Asymmetric syntheses |
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2015
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360938A (en) * | 1991-08-21 | 1994-11-01 | Union Carbide Chemicals & Plastics Technology Corporation | Asymmetric syntheses |
Non-Patent Citations (3)
| Title |
|---|
| MATTSON.: "Sustainable Catalysts for Feedstock Chemical Functionalization.", 58TH ANNUAL REPORT ON RESEARCH 2013, UNDER SPONSORSHIP OF THE ACS PETROLEUM RESEARCH FUND 52183-DNI1, vol. 1-5, 2013, XP055230082, Retrieved from the Internet <URL:https://acswebcontent.acs.org/prfar/2013/Paper12228.html> [retrieved on 20150807] * |
| SCHAFER ET AL.: "Chiral Silanediols in Anion-binding Catalysis.", ANGEW. CHEM. INT. ED., vol. 52, no. 43, 2013, pages 11321 - 11324, XP055230080, Retrieved from the Internet <URL:http://onlinelibrary.wiley.com/doi/10.1002/anie.201305496/abstract> [retrieved on 20150520] * |
| SCHAFER.: "Silanediols As Hydrogen Bond Donor Catalysts Doctor of Philosophy", CHEMISTRY, 2014, pages 1 - 286, Retrieved from the Internet <URL:https://etd.ohiolink.edu/ap/10?0::NO:10:P10_ETD_SUBID:93419> [retrieved on 20150807] * |
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