CN108558927A - A kind of silicon Stereocenter chipal compounds and its synthetic method - Google Patents
A kind of silicon Stereocenter chipal compounds and its synthetic method Download PDFInfo
- Publication number
- CN108558927A CN108558927A CN201810375689.4A CN201810375689A CN108558927A CN 108558927 A CN108558927 A CN 108558927A CN 201810375689 A CN201810375689 A CN 201810375689A CN 108558927 A CN108558927 A CN 108558927A
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- CN
- China
- Prior art keywords
- silicon
- stereocenter
- chipal compounds
- synthetic method
- silane
- Prior art date
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Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 239000010703 silicon Substances 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- -1 silane compound Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- KTQKOGBTMNDCFG-UHFFFAOYSA-N tert-butyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)C1=CC=CC=C1 KTQKOGBTMNDCFG-UHFFFAOYSA-N 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 3
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical group [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 claims description 3
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004950 trifluoroalkyl group Chemical group 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000002512 chemotherapy Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 56
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- 238000004440 column chromatography Methods 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 0 Cc1ccc(*)cc1 Chemical compound Cc1ccc(*)cc1 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical class COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
- PCJHOCNJLMFYCV-NRFANRHFSA-N (2s)-2-(9h-fluoren-9-ylmethoxycarbonylamino)-2-phenylacetic acid Chemical compound C1([C@H](NC(=O)OCC2C3=CC=CC=C3C3=CC=CC=C32)C(=O)O)=CC=CC=C1 PCJHOCNJLMFYCV-NRFANRHFSA-N 0.000 description 1
- ARHOAMSIDCQWEW-QFIPXVFZSA-N (2s)-2-(9h-fluoren-9-ylmethoxycarbonylamino)-3-(2-fluorophenyl)propanoic acid Chemical compound C([C@@H](C(=O)O)NC(=O)OCC1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1F ARHOAMSIDCQWEW-QFIPXVFZSA-N 0.000 description 1
- UGNIYGNGCNXHTR-SFHVURJKSA-N (2s)-2-(9h-fluoren-9-ylmethoxycarbonylamino)-3-methylbutanoic acid Chemical compound C1=CC=C2C(COC(=O)N[C@@H](C(C)C)C(O)=O)C3=CC=CC=C3C2=C1 UGNIYGNGCNXHTR-SFHVURJKSA-N 0.000 description 1
- SJVFAHZPLIXNDH-QFIPXVFZSA-N (2s)-2-(9h-fluoren-9-ylmethoxycarbonylamino)-3-phenylpropanoic acid Chemical compound C([C@@H](C(=O)O)NC(=O)OCC1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 SJVFAHZPLIXNDH-QFIPXVFZSA-N 0.000 description 1
- RLDJWBVOZVJJOS-AWEZNQCLSA-N (2s)-2-phenyl-2-(phenylmethoxycarbonylamino)acetic acid Chemical compound N([C@H](C(=O)O)C=1C=CC=CC=1)C(=O)OCC1=CC=CC=C1 RLDJWBVOZVJJOS-AWEZNQCLSA-N 0.000 description 1
- RNNKPNPLIMFSDY-QFIPXVFZSA-N (2s)-3-(2-chlorophenyl)-2-(9h-fluoren-9-ylmethoxycarbonylamino)propanoic acid Chemical compound C([C@@H](C(=O)O)NC(=O)OCC1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1Cl RNNKPNPLIMFSDY-QFIPXVFZSA-N 0.000 description 1
- ACFGBBASKOIPEW-QHCPKHFHSA-N (2s)-3-(2-cyanophenyl)-2-(9h-fluoren-9-ylmethoxycarbonylamino)propanoic acid Chemical compound C([C@@H](C(=O)O)NC(=O)OCC1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1C#N ACFGBBASKOIPEW-QHCPKHFHSA-N 0.000 description 1
- SZXBQTSZISFIAO-ZETCQYMHSA-N (2s)-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC(=O)OC(C)(C)C SZXBQTSZISFIAO-ZETCQYMHSA-N 0.000 description 1
- 150000005762 2-bromopyridine Chemical class 0.000 description 1
- 150000005645 2-bromoquinolines Chemical class 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MDXGYYOJGPFFJL-QMMMGPOBSA-N N(alpha)-t-butoxycarbonyl-L-leucine Chemical compound CC(C)C[C@@H](C(O)=O)NC(=O)OC(C)(C)C MDXGYYOJGPFFJL-QMMMGPOBSA-N 0.000 description 1
- KTHDTJVBEPMMGL-VKHMYHEASA-N N-acetyl-L-alanine Chemical compound OC(=O)[C@H](C)NC(C)=O KTHDTJVBEPMMGL-VKHMYHEASA-N 0.000 description 1
- KTHDTJVBEPMMGL-UHFFFAOYSA-N N-acetyl-L-alanine Natural products OC(=O)C(C)NC(C)=O KTHDTJVBEPMMGL-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XYAJTKMHJHBKOC-UHFFFAOYSA-N [Cl].CC(C)O Chemical compound [Cl].CC(C)O XYAJTKMHJHBKOC-UHFFFAOYSA-N 0.000 description 1
- DUUBOVQFIVSRDZ-UHFFFAOYSA-N acetonitrile;ethyl prop-2-enoate Chemical compound CC#N.CCOC(=O)C=C DUUBOVQFIVSRDZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ADVUTDUSOLVMJA-UHFFFAOYSA-N anisole propan-2-ol Chemical compound CC(C)O.COC1=CC=CC=C1 ADVUTDUSOLVMJA-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZSVHUITUMSDFCK-UHFFFAOYSA-N isoquinoline;quinoline Chemical compound C1=NC=CC2=CC=CC=C21.N1=CC=CC2=CC=CC=C21 ZSVHUITUMSDFCK-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- OCXNFVQUCDFUIG-UHFFFAOYSA-N propan-2-ol;prop-1-ene Chemical compound CC=C.CC(C)O OCXNFVQUCDFUIG-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
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Abstract
Invention is related to chemosynthesis technical field, to solve the problems, such as that poor, chemo-selective and stereoselectivity be not high in the presence of such as substrate applicability in current silicon Stereocenter chirality silane synthetic method, the present invention proposes a kind of silicon Stereocenter chipal compounds and its synthetic method, using alkyl diaryl nitrogen heteroaromatic rings silane compound as raw material, the silicon Stereocenter chirality silane of high enantioselectivity is synthesized with olefine reaction, mild condition, reactant are cheap, preparation method is easy.
Description
Technical field
The present invention relates to chemosynthesis technical fields, and in particular to a kind of carbon-hydrogen link asymmetry alkenyl using palladium chtalyst
Change reaction synthesis silicon Stereocenter chipal compounds and preparation method thereof.
Background technology
Silicon Stereocenter chipal compounds are similar to carbon Stereocenter chipal compounds in structure, are all containing there are four not
With the tetrahedral configuration of substituent group.But with the carbon phase of same family ratio, silicon atom radius is larger and has certain coordination ability etc.
Feature makes chiral organo-silicon compound also show the performance of unique metalloid outside some properties for retaining carbon, is easy to disappear
Rotation is not readily available.It dives since silicon Stereocenter chirality silane has in terms of chiral auxiliary, reagent, resolving agent and drug candidate
Purposes, people begin to focus on and be dedicated to explore efficient catalyst synthesis with high enantioselectivity silicon solid in
Heart chipal compounds.
It is well known that carbon-hydrogen link is a kind of chemical bond being widely present in all kinds of organic compounds.C h bond activation strategy
Increasingly important role is played in organic synthesis, be it is a kind of most directly, it is quick to build the effective of C-C keys and C- heteroatomic bonds
Method substantially increases atom economy utilization rate and combined coefficient, reduces the discharge of waste, belongs to Green Chemistry process.Closely
Lasting further investigation over year with chemist in this field, develops several efficient catalyst system and catalyzings, to specific knot
The silicon substrate substrate of structure realizes the functionalization of regioselectivity and stereoselectivity.As Kuninobu et al. utilizes enantioselectivity
C h bond priming reaction obtains in the catalyzing and synthesizing of chiral sila spiro-bisfluorene compared with quantum jump.It is prepared using the silated strategy of dehydrogenation
Organo-silicon compound are the green synthesis methods of most attraction, and by-product only has hydrogen.Based on this strategy, Kuninobu et al.
It reports use (R)-BINAP ligands and successfully constructs chirality using the reaction of rhodium catalysis hydrogen silane intramolecular order dehydrocyclization
Sila spiro-bisfluorene compound (Angew.Chem.Int.Ed., 2013,52,1520) achieves higher yield and mapping selection
Property.It is again based on the reaction of intramolecular, Hayashi etc. (J.Am.Chem.Soc., 2012,134,7305) reports palladium chtalyst
The reaction of enantioselectivity C-H function dough, screened a series of chiral phosphine ligands, discovery can using Josiphos type ligands
Obtain the Silole product with high yield and high ee values.
Although people have succeeded in the past few decades, land productivity has synthesized silicon with asymmetric carbon-hydrogen bonding functionality strategy and has stood
Body central chirality silane, but there are still such as substrate applicabilities poor, chemo-selective and the not high drawback of stereoselectivity, also
Prodigious research spatial value must synthesize chemistry and return home excavation.
Invention content
To solve to exist in current silicon Stereocenter chirality silane synthetic method, such as substrate applicability is poor, chemo-selective
The not high problem with stereoselectivity, the present invention propose a kind of silicon Stereocenter chipal compounds and its synthetic method, condition
Mildly, reactant is cheap, preparation method is easy.
The present invention is achieved by the following technical solutions：A kind of silicon Stereocenter chipal compounds, the compound
Structure such as general formula (1) shown in：
Wherein, R1It is a kind of in alkyl, R2It is a kind of in ester group, aryl, amide groups, R3, R4Separately it is selected from
Alkyl, alkoxy, aryl, halogen are a kind of in trifluoroalkyl.
Preferably, R1It is a kind of in isopropyl, butyl, sec-butyl, isobutyl group, tertiary butyl, trimethyl silicane methyl；R2
Selected from carbomethoxy, ethoxycarbonyl, butyl ester base, p-methoxyphenyl, p-nitrophenyl, p-fluorophenyl, rubigan, N- isopropyl acyls
It is a kind of in amido；R3, R4It is respectively and independently selected from methyl, tertiary butyl, methoxyl group, phenyl, trifluoromethyl is a kind of in fluorine.
The synthetic method of the silicon Stereocenter chipal compounds is using nitrogen heterocyclic ring as band on the silicon atom of homing device
There are two identical aryl by being reacted with alkene under catalyst, reaction promoter, oxidant effect.
Preferably, using azepine aryl t-butyl diphenylsilane as raw material and olefine reaction, formed with palladium salt and ligand
Complex compound be catalyst, reaction promoter and oxidant is added and reacts 36-72h at 60-100 DEG C, instead in reaction medium
Product is separated with conventional separation methods after answering, obtains silicon Stereocenter chipal compounds.
Reaction equation is as follows：
The present invention realizes silicon Stereocenter chiral compound using the intermolecular carbon-hydrogen link asymmetry olefination of palladium chtalyst
The synthesis of object, this method provide reliable and practical approach for synthesis functional group SiClx Stereocenter silane.
Preferably, alkyl diaryl azepine aryl-silane is the solution that molar concentration is 0.1-0.5mol/L, it is easy to close
At.
The alkene be selected from ethyl acrylate, methyl acrylate, butyl acrylate, to methoxy styrene, to nitro
It is a kind of in styrene, pfluorostyrene, p-chlorostyrene, n-isopropyl acrylamide, alkene and alkyl diaryl azepine aryl
The molar ratio of silane is 3~5: 1.Alkene is simple and easy to get.
The palladium salt is selected from acid chloride, two (acetylacetone,2,4-pentanedione) palladiums, palladium trifluoroacetate, four acetonitrile tetrafluoro boric acid palladiums, chlorination
A kind of in palladium, usage amount is the 5~10% of alkyl diaryl azepine aryl-silane mole.Palladium salt is transition metal.
The reaction promoter is one in potassium tert-butoxide, saleratus, potassium phosphate, cesium carbonate, copper acetate, copper fluoride
Kind, usage amount is the 10-20% of alkyl diaryl azepine aryl-silane mole.
The ligand is selected from single protection chiral amino acid, and cheap and easy to get, usage amount is alkyl diaryl azepine aryl silicon
The 10~20% of alkane mole.Have as shown in following structural preferably, single protection chiral amino acid is selected from
One kind in compound；
The reaction medium is one in Isosorbide-5-Nitrae-dioxane, acetonitrile, tert-pentyl alcohol, tetrahydrofuran, toluene, isopropanol
Kind.Usage amount is the amount for making reactant fully be reacted.
The oxidant is a kind of in silver carbonate, silver oxide, oxygen, oxidant and alkyl diaryl azepine aryl silicon
The molar ratio of alkane is 3~5: 1.
The present invention is using the alkyl diaryl nitrogen heteroaromatic rings silane compound being readily synthesized as raw material, with extensive stock or appearance
The olefine reaction easily prepared synthesizes the silicon Stereocenter chirality silane of high enantioselectivity.This method need not remove water deoxygenation, behaviour
Make simple.The silicon Stereocenter compound containing nitrogen heteroatom can be obtained under mild reaction conditions, and crude product is through too fast
Sterling, convenient post-treatment can be obtained by being concentrated under reduced pressure after fast column chromatography removal of impurities.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) reaction raw materials are cheap and easy to get, and preparation method is simple, convenient post-treatment；
(2) good yield and enantioselectivity；
(3) this method has well adapting to property for the alkene of different structure, can be in relatively mild reaction condition
Under highly selective single function is realized to the ortho position of aromatic ring.
Specific implementation mode
Below by embodiment, invention is further described in detail, raw materials used commercially available in embodiment or use
It is prepared by conventional method.
Preparation example 1：The synthesis of tert-butyl diphenyl pyridine silane
To 2- bromopyridines (15.8g, 100mmol), N, N, N are added in Shlenk bottles of 500mL ', N '-tetramethylethylenediamines
(23.2g, 200mmol) and anhydrous ether 100mL, is cooled to -78 DEG C, under nitrogen protection dropwise plus 2.5M n-BuLis-just oneself
Alkane solution (40ml, 100mmol) stirs at a temperature of this 1 hour, be added later t-butyl diphenylsilane (26mL,
100mmol).After being stirred 30 minutes at -78 DEG C, then heats up and reacted overnight naturally.It is quenched with water after reaction, uses stone
Oily ether extraction, salt water washing are concentrated, are concentrated under reduced pressure after mixture rapid column chromatography, solid obtains after being washed again with a small amount of methanol
White solid 12.7g, yield 40%.
1H NMR (400MHz, CDCl3) δ 8.89 (d, J=4.3Hz, 1H), 7.67 (d, J=6.6Hz, 4H), 7.50 (td, J
=7.6,1.5Hz, 1H), 7.44-7.31 (m, 6H), 7.28 (d, J=7.6Hz, 1H), 7.24-7.19 (m, 1H), 1.20 (s,
9H).
13C NMR (101 MHz, CDCl3) δ 164.72,149.85,136.63,134.33,133.83,132.43,
129.28,127.67,122.73,28.18,18.86.
HRMS(ESI)：m/z：[M+H]+calculated for C21H24NSi：318.1673, Found：318.1663.
Preparation example 2：The synthesis of tert-butyl diphenyl quinoline silane
To 2- bromoquinolines (20.8g, 100mmol), N, N, N are added in Shlenk bottles of 500mL ', N '-tetramethylethylenediamines
(23.2g, 200mmol) and anhydrous ether 100mL, is cooled to -78 DEG C, under nitrogen protection dropwise plus 2.5M n-BuLis-just oneself
Alkane solution (40mL, 100mmol) stirs at a temperature of this 1 hour, be added later t-butyl diphenylsilane (26mL,
100mmol).After being stirred 30 minutes at -78 DEG C, then heats up and reacted overnight naturally.It is quenched with water after reaction, uses stone
Oily ether extraction, salt water washing are concentrated, are concentrated under reduced pressure after mixture rapid column chromatography, solid obtains after being washed again with a small amount of methanol
White solid 13.9g, yield 38%.
1H NMR (400MHz, CDCl3) δ 8.44 (d, J=8.4Hz, 1H), 8.04 (d, J=8.3Hz, 1H), 7.94 (d, J
=6.4Hz, 4H), 7.85 (dd, J=13.9,7.4Hz, 2H), 7.64 (t, J=7.3Hz, 1H), 7.60-7.47 (m, 7H),
1.46 (s, 9H)
13C NMR (101MHz, CDCl3) δ 167.12,148.86,136.90,134.58,133.00,130.61,
129.45,129.06,128.27,127.83,127.22,126.82,28.29,19.34.
HRMS(ESI)：m/z：[M+H]+calculated for C25H26NSi：368.1829, Found：368.1822.
Embodiment 1：(S, E) -3- (2- (tertiary butyl (phenyl) (pyridine -2- bases) silicyl) phenyl) methyl acrylate
Synthesis
To tert-butyl diphenyl pyridine silane (317mg, 1mmol), acid chloride are added in Shlenk bottles of 50mL
(0.1mmol, 22.4mg), Salicylaldoxime (136.2mg, 0.2mmo), Fmoc-Phe-OH (77.5mg, 0.2mmol) and propylene
Isopropanol 5mL is added in sour methyl esters (0.27mL, 3.0mmol) under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, in
80 DEG C are stirred 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains white solid 108mg, yield 27%.
1H NMR (400MHz, CDCl3) δ 8.79 (d, J=4.6Hz, 1H), 7.96 (d, J=7.2Hz, 1H), 7.66 (d, J
=6.6Hz, 2H), 7.52 (d, J=7.6Hz, 1H), 7.47 (d, J=15.7Hz, 1H), 7.32 (dddd, J=32.9,25.6,
13.3,4.4Hz, 7H), 7.11 (dd, J=6.9,5.5Hz, 1H), 5.92 (d, J=15.7Hz, 1H), 3.44 (s, 3H), 1.14
(s, 9H)
13C NMR (101MHz, CDCl3) δ 166.76,164.77,149.83,147.27,141.41,137.93,
136.25,135.81,134.78,133.91,132.36,129.95,129.34,128.62,127.83,127.00,122.70,
117.93,51.23,28.47,19.20.
HRMS(ESI)：m/z：[M+H]+calculated for C25H28NO2Si：402.1884, Found：402.1884.
[α]D 20=6.89 (c=0.016, CHCl3)；m.p.115-117℃.
78%ee.Enantiomeric excess was determined by HPLC with two Chiralpak
OD-H column in series(hexanes：2-propanol=99/1,0.5mL/min, 254nm)；major
enantiomer tr=33.8min, minor enantiomer tr=31.6min.
Embodiment 2：(S, E) -3- (2- (tertiary butyl (phenyl) (pyridine -2- bases) silicyl) phenyl) ethyl acrylate
Synthesis
To being added tert-butyl diphenyl pyridine silane (317mg, 1mmol) in Shlenk bottles of 50mL, palladium bichloride (17.7mg,
0.1mmol), copper fluoride (20.2mg, 0.2mmol), CbZ-Phe-OH (59.8mg, 0.2mmol) and ethyl acrylate
Acetonitrile 5mL is added in (0.33mL, 3.0mmol) under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, in 60 DEG C of stirrings
72 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains colorless oil 125mg, yield 26%.
1H NMR (400MHz, CDCl3) δ 8.79 (d, J=4.4Hz, 1H), 7.95 (d, J=7.2Hz, 1H), 7.68 (d, J
=6.5Hz, 2H), 7.54 (d, J=7.6Hz, 1H), 7.49 (d, J=15.7Hz, 1H), 7.41-7.21 (m, 7H), 7.21-
7.14 (m, 1H), 7.10 (dd, J=7.0,5.4Hz, 1H), 5.92 (d, J=15.7Hz, 1H), 3.87 (q, J=7.1Hz, 2H),
1.14 (s, 9H), 1.02 (t, J=7.1Hz, 3H)
13C NMR (101MHz, CDCl3) δ 166.32,164.83,149.78,146.88,141.38,137.92,
136.26,135.80,134.80,133.90,132.39,129.96,129.33,128.62,127.81,126.94,122.69,
118.38,60.00,28.48,19.17,14.11.
HRMS(ESI)：m/z：[M+H]+calculated for C26H30NO2Si：416.2040, Found：416.2047.
[α]D 20=10.03 (c=0.017, CHCl3).
82%ee.Enantiomeric excess was determined by HPLC with two Chiralpak
OD-H column in series(hexanes：2-propanol=99/1,0.5mL/min, 254nm)；major
enantiomcr tr=30.8min, minor enantiomer tr=28.6min.
Embodiment 3：(S, E) -3- (2- (tertiary butyl (phenyl) (pyridine -2- bases) silicyl) phenyl) butyl acrylate
Synthesis
To tert-butyl diphenyl pyridine silane (317mg, 1mmol), two (acetylacetone,2,4-pentanedione) palladiums are added in Shlenk bottles of 50mL
(15.2mg, 0.05mmol), potassium tert-butoxide (11.2mg, 0.1mmol), Boc-Val-OH (21.7mg, 0.1mmol), silver carbonate
Tert-pentyl alcohol 5mL is added in (0.82g, 3mmol) and butyl acrylate (0.64mL, 5.0mmol), after being stirred at room temperature 30 minutes, in
100 DEG C are stirred 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains white solid 164mg, yield 37%.
1H NMR (400MHz, CDCl3) δ 8.80 (d, J=4.0Hz, 1H), 7.94 (d, J=7.1Hz, 1H), 7.68 (d, J
=6.5Hz, 2H), 7.55 (d, J=7.5Hz, 1H), 7.47 (d, J=15.7Hz, 1H), 7.42-7.21 (m, 6H), 7.17 (t, J
=3.2Hz, 1H), 7.14-7.07 (m, 1H), 5.93 (d, J=15.7Hz, 1H), 3.82 (t, J=6.6Hz, 2H), 1.41-
1.31 (m, 2H), 1.14 (s, 9H), 1.12-1.08 (m, 2H), 0.82 (t, J=7.3Hz, 3H)
13C NMR (101MHz, CDCl3) δ 166.37,164.80,149.74,146.66,141.51,137.88,
136.25,135.65,134.74,133.85,132.35,129.95,129.30,128.57,127.75,126.99,122.65,
118.58,63.91,30.57,28.45,19.11,19.05,13.75.
HRMS(ESI)：m/z：[M+H]+calculated for C28H34NO2Si：444.2353, Found：444.2361.
[α]D 20=22.78 (c=0.014, CHCl3)；m.p.83-85℃.
47%ee.Enantiomeric excess was determined by HPLC with a Phenomenex
Lux 5u Cellulose-1 column(hexanes：2-propanol=99/1,0.5mL/min, 260nm)；major
enantiomer tr=14.5min, minor enantiomer tr=13.6min.
Embodiment 4：(S, E) -2- (tertiary butyl (2- (4- methoxyl-styrenes) phenyl) (phenyl) silicyl) pyridine
To tert-butyl diphenyl pyridine silane (317mg, 1mmol), palladium trifluoroacetate are added in Shlenk bottles of 50mL
(33.2mg, 0.1mmol), cesium carbonate (65.0mg, 0.2mmol), Fmoc-Phe (2-F)-OH (81.1mg, 0.2mmol) and right
Methoxy styrene (0.66mL, 5.0mmol), silver oxide (0.82g, 5mmol) are added tetrahydrofuran 10mL, are stirred at room temperature 30
After minute, stirred 48 hours in 80 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains white solid 162mg, yield 36%.
1H NMR (400MHz, CDCl3) δ 8.79 (d, J=4.4Hz, 1H), 7.93-7.87 (m, 1H), 7.79 (dd, J=
6.4,3.0Hz, 2H), 7.62 (d, J=7.9Hz, 1H), 7.38-7.23 (m, 5H), 7.22-7.12 (m, 2H), 7.03 (ddd, J
=17.3,8.6,6.2Hz, 1H), 6.73 (s, 1H), 6.65 (d, J=8.7Hz, 2H), 6.58 (dd, J=12.2,8.9Hz,
3H), 3.65 (s, 3H), 1.14 (s, 9H)
13C NMR (101MHz, CDCl3) δ 165.50,158.99,149.66,144.58,137.75,136.33,
135.61,133.83,132.95,132.42,130.32,129.88,129.63,129.19,127.95,127.79,127.56,
126.06,125.33,122.57,113.74,55.23,28.50,19.17.
HRMS(ESI)：m/z：[M+H]+calculated for C30H32NOSi：450.2248, Found：450.2256.
[α]D 20=36.61 (c=0.015, CHCl3)；m.p.130-133℃.
72%ee.Enantiomeric excess was determined by HPLC with two Chiralpak
OD-H column in series(hexanes：2-propanol=99/1,0.5mL/min, 254nm)；major
enantiomer tr=23.1min, minor enantiomer tr=21.9min.
Embodiment 5：(S, E) -2- (tertiary butyl (2- (4- nitrostyrolenes base) phenyl) (phenyl) silicyl) pyridine
To tert-butyl diphenyl pyridine silane (317mg, 1mmol), four acetonitrile tetrafluoro boric acids are added in Shlenk bottles of 50mL
Palladium (44.4mg, 0.1mmol), saleratus (20.0mg, 0.2mmol), Fmoc-Phe (2-Cl)-OH (84.2mg, 0.2mmol)
With p-nitrophenyl ethylene (0.38mL, 3.0mmol), toluene 2mL is added under the oxygen of an atmospheric pressure, is stirred at room temperature 30 minutes
Afterwards, it is stirred 48 hours in 80 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow solid 200mg, yield 43%.
1H NMR (400MHz, CDCl3) δ 8.78 (d, J=4.7Hz, 1H), 7.99 (d, J=7.4Hz, 1H), 7.87 (d, J
=8.8Hz, 2H), 7.81 (dd, J=6.4,2.9Hz, 2H), 7.63 (d, J=7.8Hz, 1H), 7.39 (t, J=7.2Hz, 1H),
7.35-7.24 (m, 5H), 7.15 (d, J=6.2Hz, 1H), 7.11-7.01 (m, 2H), 6.76 (d, J=8.8Hz, 2H), 6.63
(d, J=16.0Hz, 1H), 1.13 (s, 9H)
13C NMR (101MHz, CDCl3) δ 165.15,149.82,146.43,144.10,143.00,137.89,
136.34,136.29,135.37,134.44,133.88,132.34,130.05,129.44,127.93,127.49,126.61,
125.93,125.92,123.72,122.75,28.29,19.11.
HRMS(ESI)：m/z：[M+H]+calculated for C29H29N2O2Si：465.1993, Found：
465.1999.
[α]D 20=50.27 (c=0.028, CHC13)；m.p.135-138℃.
76%ee.Enantiomeric excess was determined by HPLC with a Chiralpak IA
column(hexanes：2-propanol=99/1,0.5mL/min, 300nm)；major enantiomcr tr=
18.6min, minor enantiomcr tr=15.4min
Embodiment 6：(S, E) -3- (2- (tertiary butyl (isoquinolyl-1) (phenyl) silicyl) phenyl) ethyl acrylate
To being added tert-butyl diphenyl quinoline silane (367mg, 1mmol) in Shlenk bottles of 50mL, acid chloride (22.4mg,
0.1mmol), potassium phosphate (42.4mg, 0.2mmol), Fmoc-Phe (2-CN)-OH (82.4mg, 0.2mmol) and ethyl acrylate
Isosorbide-5-Nitrae-dioxane 5mL is added in (0.33mL, 3.0mmol) under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, in
80 DEG C are stirred 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow oil 177mg, yield 38%.
1H NMR (400MHz, CDCl3) δ 8.20 (d, J=7.3Hz, 1H), 7.99 (dd, J=7.4,0.7Hz, 1H), 7.83
(d, J=8.3Hz, 1H), 7.79 (d, J=6.4Hz, 2H), 7.71-7.60 (m, 2H), 7.56 (d, J=7.7Hz, 1H), 7.51
(d, J=15.7Hz, 1H), 7.45 (t, J=7.5Hz, 1H), 7.38 (t, J=7.1Hz, 1H), 7.35-7.20 (m, 5H), 5.91
(d, J=15.7Hz, 1H), 3.68 (q, J=7.1Hz, 2H), 1.21 (s, 9H), 0.82 (t, J=7.1Hz, 3H)
13C NMR (101MHz, CDCl3) δ 166.95,166.19,148.53,146.74,141.54,138.06,
136.42,135.77,134.91,133.06,130.37,130.00,129.34,128.96,128.58,128.03,127.77,
127.70,127.01,126.90,126.76,118.60,59.87,28.46,19.52,13.84.
HRMS(ESI)：m/z：[M+H]+calculated for C30H32NO2Si：466.2197, Found：446.2207.
[α]D 20=1.85 (c=0.013, CHCl3)
91%ee.Enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column(hexanes：2-propanol=98.7/1.3,0.5mL/min, 270nm)；major enantiomer tr
=15.3min, minor enantiomer tr=13.6min.
Embodiment 7：(S, E) -3- (2- (tertiary butyl (isoquinolyl-1) (phenyl) silicyl) phenyl) butyl acrylate
To being added tert-butyl diphenyl quinoline silane (367mg, 1mmol) in Shlenk bottles of 50mL, acid chloride (22.4mg,
0.1mmol), Salicylaldoxime (36.2mg, 0.2mmol), Cbz-Phg-OH (57.0mg, 0.2mmol) and butyl acrylate
Isosorbide-5-Nitrae-dioxane 5mL is added in (0.64mL, 5.0mmol) under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, in
80 DEG C are stirred 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow oil 197mg, yield 40%.
1H NMR (400MHz, CDCl3) δ 8.20 (d, J=7.9Hz, 1H), 7.98 (dd, J=7.4,0.9Hz, 1H), 7.83
(d, J=8.3Hz, 1H), 7.81-7.77 (m, 2H), 7.66 (dd, J=14.0,7.4Hz, 2H), 7.57 (d, J=7.6Hz,
1H), 7.50 (d, J=15.7Hz, 1H), 7.46 (t, J=8.0Hz, 1H), 7.39 (t, J=7.2Hz, 1H), 7.35-7.19 (m,
5H), 5.93 (d, J=15.7Hz, 1H), 3.62 (t, J=6.7Hz, 2H), 1.20 (s, 9H), 1.19-1.10 (m, 3H), 0.96
(dq, J=14.4,7.3Hz, 2H), 0.69 (t, J=7.3Hz, 3H)
13C NMR (101MHz, CDCl3) δ 166.90,166.30,148.56,146.57,141.60,138.05,
136.40,135.66,134.88,133.04,130.43,130.01,129.32,128.93,128.59,128.01,127.74,
127.70,127.00,126.94,126.75,118.72,63.81,30.32,28.44,19.49,18.87,13.62.
HRMS(ESI)：m/z：[M+H]+calculated for C32H36NO2Si：494.2510, Found：494.2504.
[α]D 20=-2.4 (c=0.017, CHCl3)
70%ee.Enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column(hexanes：2-propanol=99/1,0.5mL/min, 270nm)；major enantiomer tr=
13.9min, minor enantiomer tr=20.6min.
Embodiment 8：(S, E) -3- (2- (tertiary butyl (isoquinolyl-1) (phenyl) silicyl) phenyl)-N- isopropyls
Acrylamide
To being added tert-butyl diphenyl quinoline silane (367mg, 1mmol) in Shlenk bottles of 50mL, acid chloride (22.4mg,
0.1mmol), saleratus (20.0mg, 0.2mmol), Boc-Leu-OH (46.2mg, 0.2mmol) and N- isopropyl acrylamides
Isopropanol 5mL is added, after being stirred at room temperature 30 minutes, in 80 DEG C in amine (0.34mL, 3.0mmol) under the oxygen of an atmospheric pressure
Stirring 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow oil 143mg, yield 30%.
1H NMR (400MHz, CDCl3) δ 8.21 (d, J=8.0Hz, 1H), 8.04 (d, J=7.1Hz, 1H), 7.97 (d, J
=6.3Hz, 2H), 7.82 (d, J=8.2Hz, 1H), 7.65 (t, J=8.4Hz, 2H), 7.54-7.25 (m, 7H), 7.19 (d, J
=8.2Hz, 1H), 6.87 (d, J=16.1Hz, 1H), 5.86 (d, J=16.2Hz, 1H), 4.39 (s, 1H), 3.63 (dq, J=
13.6,6.6Hz, 1H), 1.16 (s, 9H), 0.75 (d, J=6.5Hz, 3H), 0.58 (d, J=6.5Hz, 3H)
13C NMR (101MHz, CDCl3) δ 167.28,165.92,148.52,142.15,139.47,137.43,
136.54,135.23,134.30,133.24,130.27,129.55,129.16,127.99,127.98,127.93,127.85,
127.05,126.95,126.84,123.90,40.81,28.11,22.39,22.2,19.17.
HRMS(ESI)：m/z：[M+H]+calculated for C31H35N2OSi：479.2513, Found：479.2515.
[α]D 20=-37.41 (c=0.019, CHCl3)
91%ee.Enantiomeric excess was determined by HPLC with a Chiralpak IC
columm(hexanes：2-propanol=95/5,1.0mL/min, 270nm)；major enantiomer tr=
32.6min, minor enantiomer tr=29.1min.
Embodiment 9：(S, E) -1- (tertiary butyl (2- (4- methoxyl-styrenes) phenyl) (phenyl) silicyl) isoquinoline
Quinoline
To being added tert-butyl diphenyl quinoline silane (367mg, 1mmol) in Shlenk bottles of 50mL, acid chloride (11.2mg,
0.05mmol), Salicylaldoxime (18.1mg, 0.1mmol), Fmoc-Val-OH (33.9mg, 0.1mmol) and to methoxybenzene
Isopropanol 5mL is added, after being stirred at room temperature 30 minutes, in 80 in ethylene (0.66mL, 4.0mmol) under the oxygen of an atmospheric pressure
DEG C stirring 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow oil 259mg, yield 52%.
1H NMR (400MHz, CDCl3) δ 8.24 (s, 1H), 8.01-7.84 (m, 3H), 7.76 (d, J=8.3Hz, 1H),
7.69-7.56 (m, 3H), 7.52-7.17 (m, 7H), 6.76 (d, J=16.0Hz, 1H), 6.57 (d, J=16.0Hz, 1H),
6.50 (d, J=8.7Hz, 2H), 6.39 (d, J=8.7Hz, 2H), 3.60 (s, 3H), 1.21 (s, 9H)
13C NMR (101MHz, CDCl3) δ 167.81,158.83,148.54,144.71,137.83,136.53,
135.60,135.34,133.06,132.83,130.30,130.10,129.95,129.48,129.22,128.91,128.15,
128.11,127.75,127.44,127.06,126.64,126.05,125.26,113.60,55.17,28.4,19.55.
HRMS(ESI)：m/z：[M+H]+calculated for C34H34NOSi：500.2404, Found：500.2398.
[α]D 20=30.59 (c=0.014, CHC13)
91%ee.Enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column(hexanes：2-propanol=99/1,0.5mL/min, 210nm)；major enantiomer tr=
29.4min, minor enantiomer tr=13.3min.
Embodiment 10：(S, E) -1- (tertiary butyl (2- (4- nitrostyrolenes base) phenyl) (phenyl) silicyl) isoquinolin
To being added tert-butyl diphenyl quinoline silane (367mg, 1mmol) in Shlenk bottles of 50mL, acid chloride (11.2mg,
0.05mmol), Salicylaldoxime (18.1mg, 0.1mmol), Cbz-Val-OH (25.1mg, 0.1mmol) and p-nitrophenyl ethylene
(0.38mL, 3.0mmol) isopropanol 10mL is added under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, is stirred in 80 DEG C
It mixes 48 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow solid 278mg, yield 54%.
1H NMR (400MHz, CDCl3) δ 8.21 (d, J=8.4Hz, 1H), 8.04 (d, J=7.4Hz, 1H), 7.98-7.89
(m, 2H), 7.75 (d, J=8.3Hz, 1H), 7.71-7.61 (m, 4H), 7.57 (d, J=7.9Hz, 1H), 7.41 (t, J=
7.5Hz, 2H), 7.31 (dd, J=8.2,5.1Hz, 4H), 7.22 (d, J=8.4Hz, 1H), 7.06 (d, J=16.0Hz, 1H),
6.62 (d, J=8.7Hz, 2H), 6.56 (d, J=16.0Hz, 1H), 1.20 (s, 9H)
13C NMR (101MHz, CDCl3) δ 167.49,148.61,146.29,143.86,143.26,137.84,
136.59,136.18,135.26,134.35,133.05,130.27,130.11,129.43,129.13,127.96,127.83,
127.66,127.43,126.97,126.84,126.44,126.18,125.94,123.54,28.24,19.42.HRMS
(ESI)：m/z：[M+H]+calculated for C33H31N2O2Si：515.2149, Found：515.2166.
[α]D 20=24.25 (c=0.020, CHCl3)；m.p.88-90℃.
90%ee.Enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column(hexanes：2-propanol=98/2,1.0mL/min, 270nm)；major enantiomer tr=
28.1min, minor enantiomer tr=9.1min.
Embodiment 11：(S, E) -1- (tertiary butyl (2- (4- fluorostyryls) phenyl) (phenyl) silicyl) isoquinolin
To being added tert-butyl diphenyl quinoline silane (367mg, 1mmol) in Shlenk bottles of 50mL, acid chloride (22.4mg,
0.1mmol), Salicylaldoxime (36.2mg, 0.2mmol), Ac-Ala-OH (26.2mg, 0.2mmol) and pfluorostyrene
(0.36mL, 3.0mmol) isopropanol 10mL is added under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, is stirred in 80 DEG C
It mixes 72 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow oil 302mg, yield 62%.
1H NMR (400MHz, CDCl3) δ 8.22 (d, J=8.4Hz, 1H), 7.97 (d, J=7.4Hz, 1H), 7.94-7.87
(m, 2H), 7.75 (d, J=8.3Hz, 1H), 7.69-7.56 (m, 3H), 7.50-7.34 (m, 2H), 7.33-7.19 (m, 5H),
6.80 (d, J=16.0Hz, 1H), 6.60-6.44 (m, 5H), 1.20 (s, 9H)
13C NMR (101MHz, CDCl3) δ 167.77,163.16,160.71,148.60,144.3,137.78,136.54,
135.52,133.42 (d), 133.26,132.96,131.34 (d), 130.29,129.95,129.21,128.93,128.06,
127.70 (d), 127.60,127.40,127.02,126.67,126.39,125.48,114.97 (d), 28.37,19.47.
HRMS(ESI)：m/z：[M+H]+calculated for C33H31FNSi：488.2204, Found：488.2204.
[α]D 20=3.14 (c=0.022, CHCl3)
87%ee.Enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column(hexanes：2-propanol=99/1,0.5mL/min, 300nm)；major enantiomer tr=
29.7min, minor enantiomer tr=11.5min.
Embodiment 12：(S, E) -1- (tertiary butyl (2- (4- chlorostyrenes base) phenyl) (phenyl) silicyl) isoquinolin
To tert-butyl diphenyl quinoline silane (367mg, 1mmol), acid chloride are added in Shlenk bottles of 50mL
(0.1mmol, 22.4mg), Salicylaldoxime (36.2mg, 0.2mmol), Fmoc-Phg-OH (74.6mg, 0.2mmol) and to chlorine
Isopropanol 10mL is added in styrene (0.41mL, 3.0mmol) under the oxygen of an atmospheric pressure, after being stirred at room temperature 30 minutes, in
80 DEG C are stirred 72 hours.It is concentrated under reduced pressure after rapid column chromatography, obtains yellow oil 327mg, yield 65%.
1H NMR (400MHz, CDCl3) δ 8.21 (d, J=8.1Hz, 1H), 7.98 (d, J=7.3Hz, 1H), 7.91 (dd, J
=6.2,2.7Hz, 2H), 7.75 (d, J=8.3Hz, 1H), 7.70-7.52 (m, 3H), 7.41 (ddd, J=17.7,11.6,
4.1Hz, 2H), 7.32-7.20 (m, 5H), 6.86 (d, J=16.0Hz, 1H), 6.80 (d, J=8.4Hz, 2H), 6.51 (d, J=
16.0Hz, 1H), 6.45 (d, J=8.4Hz, 2H), 1.20 (s, 9H)
13C NMR (101MHz, CDCl3) δ 166.60,147.52,143.02,136.75,135.47,134.72,
134.40,132.39,131.93,131.52,131.10,129.23,128.92,128.22,127.92,127.19,126.98,
126.69,126.63,126.27,126.19,125.94,125.64,125.53,124.50,27.30,18.42.
HRMS(ESI)：m/z：[M+H]+calculated for C33H31ClNSi：504.1909, Found：504.1909.
[α]D 20=11.96 (c=0.028, CHCl3).
90%ee.Enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column(hexanes：2-propanol=99/1,0.5mL/min, 300nm)；major enantiomer tr=
30.2min.minor enantiomer tr=11.9min.
Claims (10)
1. a kind of silicon Stereocenter chipal compounds, which is characterized in that shown in the structure of the compound such as general formula (1)：
Wherein, R1It is a kind of in alkyl, R2It is a kind of in ester group, aryl, amide groups, R3, R4It is separately selected from alkyl,
Alkoxy, aryl, halogen are a kind of in trifluoroalkyl.
2. a kind of a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 1, which is characterized in that with
Azepine aryl t-butyl diphenylsilane is raw material and olefine reaction, and the complex compound formed using palladium salt and ligand adds as catalyst
Enter reaction promoter, oxidant, in reaction medium, 36-72h is reacted at 60-100 DEG C, isolates product after reaction, is obtained
Silicon Stereocenter chipal compounds.
3. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2, which is characterized in that alkyl two
Aryl azepine aryl-silane is the solution that molar concentration is 0.1-0.5mol/L.
4. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2 or 3, which is characterized in that alkene
Hydrocarbon be selected from ethyl acrylate, methyl acrylate, butyl acrylate, to methoxy styrene, p-nitrophenyl ethylene, to fluorophenethyl
A kind of in alkene, p-chlorostyrene, n-isopropyl acrylamide, the molar ratio of alkene and alkyl diaryl azepine aryl-silane is 3
~5: 1.
5. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2 or 3, which is characterized in that palladium
Salt is selected from one kind, usage amount in acid chloride, two (acetylacetone,2,4-pentanedione) palladiums, palladium trifluoroacetate, four acetonitrile tetrafluoro boric acid palladiums, palladium bichloride
The 5~10% of alkyl diaryl azepine aryl-silane mole.
6. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2 or 3, which is characterized in that anti-
Answer auxiliary agent a kind of in potassium tert-butoxide, saleratus, potassium phosphate, cesium carbonate, copper acetate, copper fluoride, usage amount is alkyl two
The 10-20% of aryl azepine aryl-silane mole.
7. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2 or 3, which is characterized in that match
Body is selected from single protection chiral amino acid, and usage amount is the 10~20% of alkyl diaryl azepine aryl-silane mole.
8. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 7, which is characterized in that described
Single protection chiral amino acid is selected from one kind in such as following structural compound represented；
9. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2 or 3, which is characterized in that anti-
Answer medium a kind of in Isosorbide-5-Nitrae-dioxane, acetonitrile, tert-pentyl alcohol, tetrahydrofuran, toluene, isopropanol.
10. a kind of synthetic method of silicon Stereocenter chipal compounds according to claim 2 or 3, which is characterized in that oxygen
Agent is a kind of in silver carbonate, silver oxide, oxygen, and the molar ratio of oxidant and alkyl diaryl azepine aryl-silane is 3~5
∶1。
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| CN114874251A (en) * | 2022-04-18 | 2022-08-09 | 南方科技大学 | Silicon center chiral silanol and synthetic method thereof |
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| CN111647018A (en) * | 2020-06-04 | 2020-09-11 | 杭州师范大学 | Preparation method of phosphorus center chiral compound |
| CN111647018B (en) * | 2020-06-04 | 2023-04-07 | 杭州师范大学 | Preparation method of phosphorus center chiral compound |
| CN114874251A (en) * | 2022-04-18 | 2022-08-09 | 南方科技大学 | Silicon center chiral silanol and synthetic method thereof |
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