CN107235995A - 一种手性二氢硅烷化合物及其合成方法和应用 - Google Patents
一种手性二氢硅烷化合物及其合成方法和应用 Download PDFInfo
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- CN107235995A CN107235995A CN201710433275.8A CN201710433275A CN107235995A CN 107235995 A CN107235995 A CN 107235995A CN 201710433275 A CN201710433275 A CN 201710433275A CN 107235995 A CN107235995 A CN 107235995A
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- Prior art keywords
- chiral
- phenyl
- formula
- alkyl
- methyl
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- -1 silane compound Chemical class 0.000 title claims abstract description 118
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 53
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 70
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 39
- 125000001424 substituent group Chemical group 0.000 claims description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 15
- 125000001544 thienyl group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- 125000001624 naphthyl group Chemical group 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 125000003368 amide group Chemical group 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical class C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 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 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000005493 quinolyl group Chemical group 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical class COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 4
- 150000002518 isoindoles Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 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 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910003828 SiH3 Inorganic materials 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims 2
- GQBONCZDJQXPLV-UHFFFAOYSA-N 4-aminoisoindole-1,3-dione Chemical compound NC1=CC=CC2=C1C(=O)NC2=O GQBONCZDJQXPLV-UHFFFAOYSA-N 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 150000004819 silanols Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 15
- 239000010703 silicon Substances 0.000 abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 125000004429 atom Chemical group 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 41
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 36
- 239000007788 liquid Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- CISLWSORCMBVQY-UHFFFAOYSA-N ethyl(phenyl)silane Chemical compound CC[SiH2]C1=CC=CC=C1 CISLWSORCMBVQY-UHFFFAOYSA-N 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 12
- 238000006459 hydrosilylation reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 235000019439 ethyl acetate Nutrition 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 150000002431 hydrogen Chemical class 0.000 description 6
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000004756 silanes Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- 229910019131 CoBr2 Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 0 C*C(C(C1(CC2*[C@@](C)C2)NC1C*)=C1CC2C*C2)=C(C)C(C(C)(*)*)C1=C Chemical compound C*C(C(C1(CC2*[C@@](C)C2)NC1C*)=C1CC2C*C2)=C(C)C(C(C)(*)*)C1=C 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- QEPCRAGGRXDAIP-UHFFFAOYSA-N CCC(C)[Na] Chemical compound CCC(C)[Na] QEPCRAGGRXDAIP-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- DYJFXZAVYGPICR-UHFFFAOYSA-N benzene;silicon Chemical compound [Si].C1=CC=CC=C1 DYJFXZAVYGPICR-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 2
- ORAFSRLMBKVLQW-NSHDSACASA-N (4-chlorophenyl)-[(1S)-1-phenylethyl]silane Chemical compound ClC1=CC=C(C=C1)[SiH2][C@@H](C)C1=CC=CC=C1 ORAFSRLMBKVLQW-NSHDSACASA-N 0.000 description 1
- RYVBDHIYYIYDRD-LBPRGKRZSA-N (4-methoxyphenyl)-[(1S)-1-phenylethyl]silane Chemical compound COC1=CC=C(C=C1)[SiH2][C@@H](C)C1=CC=CC=C1 RYVBDHIYYIYDRD-LBPRGKRZSA-N 0.000 description 1
- CJSATXKCHMRLCK-NSHDSACASA-N (5S)-5-phenylsilylhexan-1-ol Chemical compound C1(=CC=CC=C1)[SiH2][C@H](CCCCO)C CJSATXKCHMRLCK-NSHDSACASA-N 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
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- 238000005292 vacuum distillation Methods 0.000 description 1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C07F7/08—Compounds having one or more C—Si linkages
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种手性二氢硅烷化合物，如式IV所示，式IV中，*代表手性碳原子。并公开了手性二氢硅烷化合物的合成方法：以式I所示的烯烃和式II所示的硅烷为原料，手性CoX2‑OIP络合物为催化剂，在还原剂存在下，反应制得式IV所示的手性二氢硅烷化合物。本发明合成方法适用于多种不同类型的烯烃，反应条件温和，操作简便，原子经济性高。反应无需其他任何的有毒过渡金属盐类的加入，反应的产率也较好，一般为53％～97％，对映体选择性也较高，一般为81％～>99％。本发明提供的式IV所示的手性二氢硅烷化合物可用于合成手性醇类化合物，手性硅醇类化合物，手性多取代硅烷类化合物等。
Description
技术领域
本方法涉及一种手性二氢硅烷化合物及其合成方法和应用，尤其是涉及一种光学活性的硅烷化合物的合成方法。
背景技术
手性广泛存在于自然界中，“沙利度胺事件”使人们逐渐认识到了手性的重要性。不对称催化反应是制备手性化合物的重要途径。在不对称催化反应中，金属催化是非常重要的一个手段，但不同金属在地球上的含量是不一样的，且有些金属具有一定的毒性，因此，利用地球丰产的廉价的低毒或者无毒的金属进行不对称催化具有重要意义，尤其在药物和材料领域有广阔的应用前景。
硅氢化反应目前被广泛用于制备含有碳－碳双键、碳-碳叁键、碳-氧双键、碳-氮双键、碳-氮叁键、氮-氮双键和氮－氧键的一系列有机硅化合物[a)K.Tamao,N.Ishida,T.Tanaka,M.Kumada,Organometallics1983,2,1694；b)I.Fleming,R.Henning,H.Plaut,J.Chem.Soc.Chem.Commun.1984,29.]。硅氢化反应还在合成天然有机化合物中作保护基和还原剂等[a)Y.Hatanaka,T.Hiyama,J.Org.Chem.1988,53,918；b)S.E.Denmark,C.S.Regens,Acc.Chem.Res.2008,41,1486.]。硅材料是重要的半导体材料，有机硅化合物在生物医药领域也有重要的应用。烯烃的硅氢化反应是制备有机硅材料的重要途径。
在烯烃的硅氢化反应中，硅氢键扮演着非常重要的角色。由于硅氢键具有较高的反应活性，因此，通过对硅氢键的延伸化，可以获得更多更丰富的含硅化合物。化合物中含有较多的硅氢键，能为后续延伸化提供更多的空间。因此，含有两个硅氢键的硅烷，由于其既具有一定的取代基基础，又具有一定的硅氢键，常常被用来作为合成有机硅化合物的中间体。(Nielsen,L.；Skrydstrup,T.J.AM.CHEM.SOC.2008,130,13145–13151)
1976年，Kumada发展了烯烃的不对称硅氢化反应[Yamamoto,K.；Hayashi,T.；Zembayashi,M.；Kumada,M.J.Organomet.Chem.1976,118,161]，但是对映体选择性较低(0.6-20.9％ee)。1991年，Hayashi发展了钯催化的氯硅烷作为硅试剂的简单烯烃的不对称硅氢化反应[Uozumi,Y.；Hayashi,T.J.Am.Chem.Soc.1991,113,9887]，后来又有研究小组发展了一系列的手性膦配体应用于烯烃的不对称硅氢化反应，但是所用硅试剂都含有氯或者氟，这大大限制了其官能团容忍性[钯催化的烯烃的不对称硅氢化反应综述:a)Gibson,S.E.；Rudd,M.Adv.Synth.Catal.2007,349,781；钯催化的烯烃的不对称硅氢化反应实例：b)Uozumi,Y.；Hayashi,T.J.Am.Chem.Soc.1991,113,9887；c)Kitayama,K.；Uozumi,Y.；Hayashi,T.J.Chem.Soc.,Chem.Commun.1995,1533；d)Weber,I.；Jones,G.B.TetrahedronLett.2001,42,6983；e)Shimada,T.；Mukaide,K.；Shinohara,A.；Han,J.W.；Hayashi,T.J.Am.Chem.Soc.2002,124,1584；f)Jensen,J.F.；Svendsen,B.Y.；laCour,T.V.；Pedersen,H.L.；Johannsen,M.J.Am.Chem.Soc.2002,124,4558；g)Guo,X.；Xie,J.；Hou,G.；Shi,W.；Wang,L.；Zhou,Q.Tetrahedron:Asymmetry.2004,15,2231；h)Rendler,S.；R.；Keller,M.；Oestreich,M.Eur.J.Org.Chem.2008,2582；i)Zhang,F.；Fan,Q.Org.Biomol.Chem.2009,7,4470；j)Junge,K.；Wendt,B.；Enthaler,S.；Beller,M.ChemCatChem2010,2,453；铑催化的烯烃的不对称硅氢化反应综述:k)Ito,J.-i.；Nishiyama,H.Organomet.Chem.2011,37,185；稀有过渡金属催化的烯烃不对称硅氢化反应实例:l)Fu,P.-F.；Brard,L.；Li,Y.；Marks,T.J.J.Am.Chem.Soc.1995,117,7157；m)Gountchev,T.I.；Tilley,T.D.Organometallics 1999,18,5661.].Tamao和Bosnich分别独立地发展了以硅烷作为硅试剂的分子内烯烃不对称硅氢化反应[a)Tamao,K.；Tohma,T.；Inui,N.；Nakayama,O.；Ito,Y.Tetrahedron Lett.1990,31,7333.b)Bergens,S.H.；Noheda,P.；Whelan,J.；Bosnich,B.J.Am.Chem.Soc.1992,114,2121.]。除此之外，对于利用不含卤素的硅烷作为硅试剂的分子间烯烃不对称硅氢化反应，只有以环乙烯基酯或降冰片烯为底物的几个例子(a)M.B.Haque,B.P.Roberts,D.A.Tocher,J.Chem.Soc.,PerkinTrans.I 1998,2881；b)T.I.Gountchev,T.D.Tilley,Organometallics 1999,18,5661.)，或者是1,1-二取代烯烃的马氏加成硅氢化反应，但其只有中等的ee值(P.-F.Fu,L.Brard,Y.Li,T.J.Marks,J.Am.Chem.Soc.1995,117,7157)。2012年，Nishiyama and co-workers报道了铑催化的以三取代硅烷作为硅试剂的烯烃不对称硅氢化反应，但大多情况下其只有中等的区域选择性(30/70～91/9b/l)(T.Naito,T.Yoneda,J.-i.Ito,H.Nishiyama,Synlett,2012,23,2957.)。2017年，Lu group报道了炔烃的不对称硅氢化/氢化串联反应来合成手性硅化合物，但其对于脂肪族的底物是不适用的，而且只能合成三取代的手性硅化合物。(Guo,J.；Shen,X.；Lu,Z.Angew.Chem.Int.Ed.2017,56,615.)随后，Buchwald group报道了手性双膦配体、铜催化的烯烃不对称硅氢化反应，但其需要用到过量的硅烷(1.5～5equiv)反应12-72小时，且其手性二取代的硅氢化产物只能作为中间体通过Tamao氧化转化为手性醇化合物，此外，对于脂肪族的底物也是不适用的。(GribbleJr.,M.W.；Pirnot,M.T.；Bandar,J.S.；Liu,R.Y.；Buchwald,S.L.J.Am.Chem.Soc.2017,139,2192.)
因此，发展高效率高选择性的地球丰产金属催化的烯烃的不对称硅氢化反应合成手性二氢硅烷化合物有着重大的意义。
发明内容
本发明要解决的问题是提供一种有效合成手性二氢硅烷化合物的方法，是由手性CoX2-OIP络合物催化烯烃和硅烷的硅氢化反应，高效率高对映体选择性地合成光学活性的二氢硅烷化合物的方法。
本发明是通过以下技术方案来实现的：
一种手性二氢硅烷化合物，所述手性二氢硅烷化合物如式IV所示：
式IV中，*代表手性碳原子；
R1,R2任选自C1-C16的烷基、C3-C16的环烷基、苄基、萘基、邻苯二甲酰亚胺基、式V所示的基团或C4～C10的含N、O、S的杂环芳基A；所述烷基、环烷基上的H不被取代或被1个以上的取代基A取代，所述取代基A包括硝基、卤素、苯基、邻苯二甲酰亚胺基、杂环芳基B、甲氧羰基、羰基、三氟甲基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；所述杂环芳基B包括吲哚基、噻吩基、吡啶基或喹啉基；所述苄基、萘基、含N、O、S的杂环芳基A上的H不被取代或被1个以上的取代基B取代，所述取代基B包括C1～C3的烷基、C1～C3的烷氧基、硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基或邻苯二甲酰亚胺基；所述含N、O、S的杂环芳基A包括噻吩基、苯并噻吩基、吲哚基、N-甲基吲哚基、吡啶基、喹啉基或呋喃基；
式V中，R3、R4、R5、R6、R7任选自H、卤素、C1-C16的烷基、C1-C16的烷氧基、C1-C16的烷硫基、苯基、三氟甲基、甲氧羰基、硝基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基、乙酰氧甲基、2-甲基-1,3-二氧环戊基中的任意一种。
进一步，优选所述R1为C1-C10的烷基、萘基、N-甲基吲哚基、噻吩基、苯并噻吩基、吡啶基、2-甲氧基吡啶基或式V所示的基团；所述烷基的H不被取代或被1个以上的取代基A取代，所述取代基A为硝基、卤素、苯基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、邻苯二甲酰亚胺基、吲哚基、噻吩基或吡啶基；
优选R2为式V所示的基团；
式V所示的基团优选为苯基或含有1～2个以下取代基的取代苯基：甲基、丁基、苯基、甲氧基、甲硫基、F、Cl、Br、三氟甲基、甲氧羰基、乙酰氧甲基、2-甲基-1,3-二氧环戊基。
更进一步，优选所述R1为苯基、对甲基苯基、对丁基苯基、联苯基、对甲氧基苯基、对甲硫基苯基、对氟苯基、对氯苯基、对溴苯基、对三氟甲基苯基、对甲氧羰基苯基、对乙酰氧甲基苯基、4-(2-甲基-1,3-二氧环戊基)苯基、间三氟甲基苯基、间氯苯基、间甲基苯基、邻甲基苯基、3-甲氧基-4-氟苯基、1-萘基、2-萘基、N-甲基吲哚基、噻吩基、苯并噻吩基、2-甲氧基吡啶基、CH3(CO)CH2CH2-、正己基、溴代丙基、1-羟基-丁基或异吲哚-1,3-二酮取代的壬基。
优选R2为苯基、对甲氧基苯基或对氯苯基。
本发明还提供所述手性二氢硅烷化合物的合成方法，所述方法为：以式I所示的烯烃和式II所示的硅烷为原料，手性CoX2-OIP络合物为催化剂，在还原剂存在下，反应制得式IV所示的手性二氢硅烷化合物；
R2SiH3 II
式I或式II中，R1,R2任选自C1-C16的烷基(优选C1-C10的烷基，更优选C1-C6的烷基)、C3-C16的环烷基(优选C3-C10的环烷基，更优选C3-C6的环烷基)，苄基、萘基、邻苯二甲酰亚胺基、式V所示的基团或C4～C10的含N、O、S的杂环芳基A；所述含N、O、S的杂环芳基A包括噻吩基、苯并噻吩基、吲哚基、N-甲基吲哚基、吡啶基、喹啉基、呋喃基等；所述烷基、环烷基上的H不被取代或被1个以上的取代基A取代，所述取代基A包括硝基、卤素、苯基、邻苯二甲酰亚胺基、杂环芳基B、甲氧羰基、羰基、三氟甲基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；所述杂环芳基B包括吲哚基、噻吩基、吡啶基、喹啉基等；所述苄基、萘基、含N、O、S的杂环芳基A上的H不被取代或被1个以上的取代基B取代，所述取代基B包括C1～C3的烷基、C1～C3的烷氧基、硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基或邻苯二甲酰亚胺基；
式V中，R3、R4、R5、R6、R7任选自H、卤素、C1-C16的烷基(优选C1-C10的烷基，更优选C1-C6的烷基)、C1-C16的烷氧基(优选C1-C10的烷氧基，更优选C1-C6的烷氧基)、C1-C16的烷硫基(优选C1-C10的烷硫基，更优选C1-C6的烷硫基)、苯基、三氟甲基、甲氧羰基、硝基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基、乙酰氧甲基、2-甲基-1,3-二氧环戊基中的任意一种。卤素包括F、Cl、Br或I；R3，R4，R5，R6,R7全为H时，式V所示的基团即为苯基；
优选式V所示的基团为苯基或含有1～2个以下取代基的取代苯基：甲基、丁基、苯基、甲氧基、甲硫基、F、Cl、Br、三氟甲基、甲氧羰基、乙酰氧甲基、2-甲基-1,3-二氧环戊基
进一步，优选R1为C1-C10的烷基、萘基、N-甲基吲哚基、噻吩基、苯并噻吩基、吡啶基、2-甲氧基吡啶基式V所示的基团；所述烷基的H不被取代或被1个以上的取代基A取代，所述取代基A优选硝基、卤素、苯基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、邻苯二甲酰亚胺基、吲哚基、噻吩基、吡啶基等；
优选R2为式V所示的基团。
进一步，优选R1为苯基、对甲基苯基、对丁基苯基、联苯基、对甲氧基苯基、对甲硫基苯基、对氟苯基、对氯苯基、对溴苯基、对三氟甲基苯基、对甲氧羰基苯基、对乙酰氧甲基苯基、4-(2-甲基-1,3-二氧环戊基)苯基、间三氟甲基苯基、间氯苯基、间甲基苯基、邻甲基苯基、3-甲氧基-4-氟苯基、1-萘基、2-萘基、N-甲基吲哚基、噻吩基、苯并噻吩基、2-甲氧基吡啶基、CH3(CO)CH2CH2-、、1-羟基-丁基、正己基、溴代丙基或异吲哚-1,3-二酮取代的壬基。
优选R2为苯基、对甲氧基苯基或对氯苯基
本发明所用的催化剂为手性CoX2-OIP络合物(OIP：亚胺吡啶噁唑啉配体)，结构式为式III所示的化合物或其对映体，所述对映体即为式III的镜像。R8，R9,R10,R11,R12,R13,R14,R15,R16,R17,R18,R19任选自H、C1-C16的烷基、C1-C16的烷氧基、卤素、苯基、萘基或苄基：所述烷基、烷氧基上的H不被取代或被1个以上的取代基C取代，所述取代基C包括硝基、卤素、苯基、甲氧羰基、羰基、三氟甲基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；
所述苯基、苄基、萘基上的H不被取代或被1个以上的取代基D取代，所述取代基D包括C1～C3的烷基、C1～C3的烷氧基、硝基、卤素、苯基、甲氧羰基、羰基、三氟甲基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；
X为F、Cl、Br、I、OAc、CF3SO3中的任意一种。
进一步，式III中，优选R8为C1-C4的烷基或苄基、R9为C1-C4的烷基或二苯基次甲基(-CHPH2)，R10为H，R11为C1-C4的烷基、C1-C4的烷氧基或卤素；R12为H；R13为C1-C4的烷基或二苯基次甲基(-CHPH2)；R14为甲基；R15、R16、R17、R18、R19均为H，X优选为Cl。
更优选的，所用的催化剂如式III-1所示
Bn代表苄基，Ph代表苯基，MeO代表甲氧基；
本发明合成方法的反应式如下所示
作为进一步地改进，本发明所述的所述合成方法可在无溶剂或在有机溶剂中进行，在有机溶剂中反应时，所述的有机溶剂可以为苯、四氯化碳、甲苯、四氢呋喃、乙醚、二氯甲烷、乙腈、二氧六环、石油醚、环己烷、正己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中的任意一种，优选乙醚。
所述有机溶剂的体积用量一般以式I所示的烯烃的物质的量计为1～10mL/mmol。
作为进一步地改进，本发明所述的所述合成方法中优选在无溶剂条件下或乙醚溶剂中进行。
作为进一步地改进，本发明所述的式II所示的硅烷、式I所示的烯烃、手性CoX2-OIP络合物、还原剂的物质的量之比为1：0.1-10：0.0000005-0.05：0.0000005-0.15，优选为1：0.1-10：0.0005-0.05：0.0015-0.15，更优选为1：0.5-2：0.001-0.05：0.001-0.15；最优选为1：1～1.2：0.01～0.05：0.03～0.15。
作为进一步地改进，本发明所述的所述合成方法中，反应温度为-30℃～80℃，优选-10℃～60℃，尤其推荐0～25℃。
本发明反应的反应时间优选3分钟-48小时，优选为30分钟-12小时，尤其推荐1小时
本发明的还原剂为三乙基硼氢化钠、三仲丁基硼氢化钠、三乙基硼氢化锂、叔丁醇钠、叔丁醇钾、叔丁醇锂、叔戊醇钠、乙醇钠、甲醇钠、甲醇钾中的任意一种，优选三乙基硼氢化钠、叔丁醇钠、乙醇钠或甲醇钠，更优选为叔丁醇钠。
作为进一步地改进，本发明反应结束后，所得粗产物经过后处理制得式IV所示的手性二氢硅烷化合物，进一步，所述后处理方法为下列一种或两种以上：重结晶、薄层层析、柱层析或减压蒸馏，优选为柱层析。
本发明方法提供了一种有效的由手性CoX2-OIP络合物为催化剂，由烯烃和硅烷高效率高对映体选择性的合成光学活性的硅烷化合物的方法。与现有方法相比，该方法适用于多种不同类型的烯烃，反应条件温和，操作简便，原子经济性高。另外，反应无需其他任何的有毒过渡金属(如钌、铑、钯等)盐类的加入，在药物和材料合成上具有较大的实际应用价值。且反应的产率也较好，一般为53％～97％，对映体选择性也较高，一般为81％～>99％。
本发明方法制得的式IV所示的手性二氢硅烷化合物可用于氧化合成手性醇类化合物，手性硅醇类化合物，手性多取代硅烷类化合物等。常规外消的二氢硅烷化合物用于合成醇类化合物、硅醇类化合物、多取代硅烷类化合物都属于公知的方法，本发明合成出来的手性二氢硅烷同样适用，只是以手性二氢硅烷为原料代替外消原料，可以合成出相应手性的产物，因此本申请的手性二氢硅烷可进一步用于光学活性的有机硅化合物的合成，具有较大的应用价值。
进一步，所述式IV所示的手性二氢硅烷化合物用于氧化合成手性醇类化合物，所述应用的方法是将式IV所示的手性二氢硅烷经Tamao氧化，反应得到如式A所示的手性醇类化合物。反应式如下式所示：
进一步，所述Tamao氧化的反应条件一般为：式IV所示的手性二氢硅烷与四氟硼酸-乙醚络合物催化剂搅拌反应后，再与氟化钾、碳酸氢钾、双氧水反应，制得式A所示的手性醇类化合物；
进一步，优选所述Tamao氧化的反应步骤为：式IV所示的手性二氢硅烷与四氟硼酸-乙醚络合物催化剂在二氯甲烷溶剂中，在0℃搅拌反应3h，除去溶剂，加入四氢呋喃、甲醇、氟化钾、碳酸氢钾、双氧水，室温搅拌反应15h,加水稀释，乙醚萃取、洗涤、干燥后，除去溶剂后经柱层析分离制得式A所示的手性醇类化合物；所述式IV所示的手性二氢硅烷、四氟硼酸-乙醚络合物、氟化钾、碳酸氢钾、H2O2的物质的量之比为1:5～8：4～5：10:40～50
进一步，所述式IV所示的手性二氢硅烷化合物用于合成手性硅醇类化合物，所述应用的方法包括以下两种：
(1)式IV所示的手性二氢硅烷化合物在三氯化硼催化剂的作用下，反应得到式B所示的手性一羟基硅烷化合物；反应溶剂通常为二氯甲烷和水
(2)式IV所示的手性二氢硅烷化合物在钯碳催化剂的作用下，反应得到式C所示的手性二羟基硅烷化合物；反应溶剂通常为乙醚和水
反应式如下所示：
进一步，所述式IV所示的手性二氢硅烷化合物用于手性多取代硅烷类化合物，所述应用的方法包括以下两种：
(1)将式IV所示的手性二氢硅烷化合物与式D所示的烯基化合物反应，在金属络合物催化剂和还原剂作用下，反应得到如式E或式F所示的手性多取代硅烷类化合物；
(2)将式IV所示的手性二氢硅烷化合物与式G所示的炔基化合物反应，在金属络合物催化剂和还原剂作用下，反应得到如式H或式J所示的手性多取代烯基硅烷类化合物；
所述的金属络合物催化剂优选iPrOIP-FeCl2、Xantphos-CoBr2或2,4-DMBOIP.CoBr2等。
所述的还原剂为三乙基硼氢化钠、三仲丁基硼氢化钠、三乙基硼氢化锂、叔丁醇钠、叔丁醇钾、叔丁醇锂、叔戊醇钠、乙醇钠、甲醇钠、甲醇钾中的任意一种，优选三乙基硼氢化钠
反应式如下式所示：
本发明的方法是一种有效的由烯烃和硅烷合成手性二氢硅烷化合物的方法。该方法是用CoX2-OIP络合物作为催化剂，尤其是以手性的CoX2-OIP络合物作为催化剂时能够由烯烃和硅烷高效率高对映体选择性的合成光学活性的二氢硅烷化合物。
附图说明
图1催化剂手性CoX2-OIP络合物III-1的单晶结构图。
具体实施方式
下面通过具体实施例对本发明的技术方案作进一步地具体说明，但本发明的保护范围不限于此：
实施例1：手性CoX2-OIP络合物催化的烯烃和硅烷的硅氢化反应
室温下，在一干燥的反应试管中加入手性CoX2-OIP络合物(0.01mmol)，式I所示的烯烃(1.0mmol)，式II所示的硅烷(1.0mmol)，乙醚(2mL)，叔丁醇钠(0.03mmol)，然后在室温或0℃下搅拌1小时后柱层析分离(洗脱溶剂为石油醚或石油醚和乙酸乙酯的混合物)得到产物。
实施例1中，手性CoX2-OIP络合物的化学式如下式III-1所示：
制备方法参考文献：(a)Dai,S.；Sui,X.；Chen,C.Angew.Chem.Int.Ed.2015,54,9948-9953.(b)Greenhalgh,M.D.；Thomas,S.P.J.Am.Chem.Soc.,2012,134,11900-11903.(c)Leonard,W.R.；Romine,J.L.；Meyers,A.I.J.Org.Chem.1991,56,1961-1963.(d)Xi,T.；Mei,Y.C.；Lu,Z.Org.Lett.2015,17,5939-5941.(e)Guo,J.；Shen,X.Z.；Lu,Z.Angew.Chem.Int.Ed.2017,56,615-618.
具体制备方法如下：
将2,6-二二苯甲基-4-甲氧基苯胺(4.6g,10mmol)(参照文献(a)做出)，2-溴-6-乙酰基吡啶(2.4g,12mmol)，对甲苯磺酸一水合物(0.19g,1mmol)，60mL甲苯放入100mL圆底烧瓶中，圆底烧瓶接分水器，在150℃加热回流24h，冷却至室温，抽滤除去对甲苯磺酸。利用旋转蒸发除去滤液中的溶剂，残留物加入60mL乙醇，-25℃下搅拌，固体析出后抽滤，用10mL乙醇洗涤2次，得到黄色固体VI(4.92g,7.7mmol,77％产率)。熔点：177-178℃；IR:3060,3026,2924,1643,1598,1552,1450,1305；1H NMR(CDCl3,400MHz):δ7.91(d,J＝7.6Hz,1H),7.58-7.47(m,2H),7.25-7.12(m,12H),7.01(dd,J＝8.0,7.2Hz,8H),6.44(s,2H),5.21(s,2H),3.55(s,3H),1.13(s,3H)；13C NMR:(CDCl3,100MHz):δ169.1,157.1,155.2,143.2,142.1,141.7,140.7,138.4,133.4,129.7,129.4,129.0,128.3,128.0,126.4,126.1,120.0,113.7,55.1,52.2,16.8；HRMS(EI)calculated for[C40H33N2OBr]+,requires m/z636.1776found m/z 636.1775.
在氮气保护下，向干燥的Schlenk管中加入VI(2.55g,4.0mmol),醋酸钯(0.023g,0.10mmol),1,2-双二苯基膦乙烷(0.051g,0.13mmol),叔丁醇锂(0.66g,8.3mmol)，1,4-二氧六环(25mL)和(S)-4-苄基-4,5-二氢噁唑啉(0.79g,4.9mmol)(参照文献(c)做出)。Schlenk管用液氮脱气三次，反应混合物在110℃油浴中搅拌42小时，然后冷却到室温，倒入放有硅胶的砂芯抽滤，二氯甲烷淋洗(10mL×3)。旋转蒸发移除溶剂后，用石油醚：乙酸乙酯(10:1)混合溶剂作为流动相，硅胶作为固定相，进行柱层析色谱分离得到黄色固体VII(1.79g,2.5mmol,62％产率)。熔点：77-78℃；IR:2956,2924,1641,1459,1373；1H NMR(CDCl3,400MHz):δ8.08(dd,J＝8.0,10.8Hz,2H),7.76(dd,J＝8.0,7.6Hz,1H),7.35-7.23(m,5H),7.23-7.10(m,12H),7.00(d,J＝6.8Hz,8H),6.45(s,2H),5.25(s,2H),4.71-4.60(m,1H),4.45(dd,J＝8.8,9.2Hz,1H),4.25(t,J＝8.0Hz,1H),3.55(s,3H),3.30(dd,J＝5.2,14Hz,1H),2.78(dd,J＝9.2,14Hz,1H),1.45(s,3H)；13C NMR:(CDCl3,100MHz):δ169.5,163.4,156.1,155.1,145.7,143.1,142.4,142.4,141.9,137.8,136.6,133.5,133.4,129.7,129.4,129.3,128.6,128.3,128.0,126.6,126.3,126.1,125.2,123.2,113.7,107.7,72.5,68.1,55.1,52.2,46.7,41.7,16.9；HRMS(EI)calculated for[C50H43N3O2]+,requires m/z 717.3355found m/z 717.3356
在N2保护下，向干燥的Schlenk管中加入VII(1.51g,2.1mmol)，THF(25mL)，CoCl2(0.25g,1.9mmol)。反应混合物在25℃下搅拌13h后，注射25mL乙醚进入反应混合物，继续搅拌2h。反应混合物过滤，固体用乙醚(50mL)洗涤，在真空下干燥，得到棕色粉末(1.34g,1.6mmol,83％产率)。
III-1的单晶结构如图1所示，CCDC号：1542890
IV-1:(S)-1-苯基乙基苯硅烷
(S)-Phenyl(1-phenylethyl)silane
油状液体，87％产率，[α]20 D＝-18.1(c 0.94,CHCl3),99.3％ee，IR(cm-1):3023,2955,2924,2137,1600,1457.1H NMR(CDCl3,400MHz):δ7.44-7.35(m,3H),7.34-7.28(m,2H),7.28-7.21(m,2H),7.16-7.06(m,3H),4.35-4.29(m,2H),2.67-2.57(m,1H),1.45(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ144.5,135.6,131.4,129.7,128.4,127.8,127.1,125.0,25.4,16.4.HRMS(EI)calculated for[C14H16Si]+requiresm/z 212.1021,found m/z212.1019.
IV-2:(S)-1-对甲苯基乙基苯硅烷
(S)-Phenyl(1-(p-tolyl)ethyl)silane
油状液体，86％yield，[α]20 D＝-18.1(c 1.11,CHCl3),99.5％ee,IR(cm-1):3018,2954,2135,1511,1456,1014.1H NMR(CDCl3,400MHz):δ7.45-7.35(m,3H),7.34-7.28(m,2H),7.07(d,J＝8.0Hz,2H),7.00(d,J＝8.0Hz,2H),4.33-4.27(m,2H),2.62-2.53(m,1H),2.31(s,3H),1.43(d,J＝7.4Hz,3H)；13C NMR:(CDCl3,100MHz):δ141.4,135.6,134.4,131.6,129.7,129.1,127.8,127.0,24.8,20.9,16.6.HRMS(EI)calculated for[C15H18Si]+requires m/z 226.1178,found m/z 226.1175.
IV-3:(S)-1-((对叔丁基苯基)乙基)苯硅烷
(S)-(1-(4-(Tert-butyl)phenyl)ethyl)(phenyl)silane
油状液体，87％yield，[α]20 D＝-12.4(c 0.98,CHCl3),99.6％ee,IR(cm-1):2959,2135,1512,1459,1116.1H NMR(CDCl3,400MHz):δ7.44-7.35(m,3H),7.33-7.25(m,4H),7.04(d,J＝8.4Hz,2H),4.34-4.27(m,2H),2.64-2.54(m,1H),1.44(d,J＝7.6Hz,3H),1.31(s,9H)；13C NMR:(CDCl3,100MHz):δ147.7,141.3,135.6,131.7,129.7,127.8,126.7,125.2,34.3,31.4,24.6,16.4.HRMS(EI)calculated for[C18H24Si]+requires m/z 268.1647,found m/z 268.1645.
IV-4:(S)-1-(4-苯基苯基)乙基苯硅烷
(S)-(1-([1,1'-Biphenyl]-4-yl)ethyl)(phenyl)silane
白色固体，88％yield，熔点:89-91℃，Optical Rotation:[α]20 D＝-18.7(c 1.13,CHCl3),99.7％ee,IR(cm-1):2955,2924,2132,1461,1378,1119.1H NMR(CDCl3,400MHz):δ7.61-7.55(m,2H),7.49(d,J＝8.4Hz,2H),7.46-7.36(m,5H),7.35-7.28(m,3H),7.16(d,J＝7.8Hz,2H),4.39-4.32(m,2H),2.71-2.62(m,1H),1.49(d,J＝7.4Hz,3H)；13C NMR:(CDCl3,100MHz):δ143.7,141.0,137.8,135.7,131.3,129.8,128.7,127.9,127.5,127.0,126.9,126.8,25.1,16.3.HRMS(EI)calculated for[C20H20Si]+requires m/z 288.1334,found m/z 288.1334.
IV-5:(S)-1-(4-甲氧基苯基)乙基苯硅烷
(S)-(1-(4-Methoxyphenyl)ethyl)(phenyl)silane
油状液体，84％yield，[α]20 D＝-19.5(c 1.16,CHCl3).99.4％ee,IR(cm-1):2954,2926,2136,1510,1247,1116.1H NMR(CDCl3,400MHz):δ7.43-7.35(m,3H),7.33-7.27(m,2H),7.01(d,J＝8.8Hz,2H),6.80(d,J＝8.8Hz,2H),4.33-4.28(m,2H),3.78(s,3H),2.59-2.51(m,1H),1.42(d,J＝7.4Hz,3H)；13C NMR:(CDCl3,100MHz):δ157.2,136.5,135.6,131.5,129.7,127.9,127.8,113.8,55.2,24.2,16.7.HRMS(EI)calculated for[C15H18OSi]+requires m/z 242.1127,found m/z 242.1129.IV-6:(S)-1-(4-甲硫基苯基)乙基苯硅烷
(S)-(1-(4-(Methylthio)phenyl)ethyl)(phenyl)silane
油状液体，87％yield，[α]20 D＝-19.7(c 1.26,CHCl3).99.3％ee,IR(cm-1):2955,2922,2136,1492,1117.1H NMR(CDCl3,400MHz):δ7.44-7.35(m,3H),7.34-7.28(m,2H),7.17(d,J＝8.0Hz,2H),7.02(d,J＝8.0Hz,2H),4.33-4.29(m,2H),2.63-2.53(m,1H),2.46(s,3H),1.43(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ141.7,135.6,134.2,131.1,129.7,127.8,127.6,127.3,24.9,16.4,16.3.HRMS(EI)calculated for[C15H18SSi]+requires m/z258.0898,found m/z 258.0896.
IV-7:(S)-1-(4-氟苯基)乙基苯硅烷
(S)-(1-(4-fluorophenyl)ethyl)(phenyl)silane
油状液体,83％yield，[α]20 D＝-15.5(c 0.82,CHCl3),99.0％ee,IR(cm-1):2955,2925,2138,1507,1229.1H NMR(CDCl3,400MHz):δ7.44-7.35(m,3H),7.35-7.27(m,2H),7.06-6.97(m,2H),6.97-6.88(m,2H),4.30(d,J＝3.2Hz,2H),2.66-2.54(m,1H),1.43(d,J＝7.2Hz,3H).13C NMR:(CDCl3,100MHz):δ160.7(d,J＝241.4Hz,1C),140.1(d,J＝2.9Hz,1C),135.6,131.1,129.8,128.3(d,J＝7.3Hz,1C),127.9,115.1(d,J＝21.1Hz,1C),24.6,16.6.19F NMR:(376.5MHz,CDCl3)δ-118.7；HRMS(EI)calculated for[C14H15FSi]+requiresm/z 230.0927,found m/z 230.0925.
IV-8:(S)-1-(4-氯苯基)乙基苯硅烷
(S)-(1-(4-Chlorophenyl)ethyl)(phenyl)silane
白色固体，86％yield，熔点:41-42℃.[α]20 D＝-16.3(c 1.12,CHCl3),99.8％ee,IR(cm-1):2955,2924,2139,1490,1459.1H NMR(CDCl3,400MHz):δ7.42-7.36(m,3H),7.35-7.28(m,2H),7.20(d,J＝8.0Hz,2H),7.00(d,J＝8.0Hz,2H),4.30(d,J＝3.2Hz,2H),2.64-2.54(m,1H),1.43(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ143.1,135.6,130.8,130.6,129.9,128.4,128.4,127.9,25.0,16.3.HRMS(EI)calculated for[C14H15ClSi]+requires m/z 246.0632,found m/z 246.0628.
IV-9:(S)-1-(4-溴苯基)乙基苯硅烷
(S)-(1-(4-Bromophenyl)ethyl)(phenyl)silane
油状液体，83％yield，[α]20 D＝-14.8(c 0.75,CHCl3),99.4％ee,IR(cm-1):2955,2925,2138,1486,1458,1116.1H NMR(CDCl3,400MHz):δ7.43-7.28(m,7H),6.94(d,J＝8.0Hz,2H),4.30(d,J＝3.2Hz,2H),2.62-2.53(m,1H),1.43(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ143.6,135.6,131.3,130.8,129.9,128.8,127.9,118.5,25.0,16.2.HRMS(EI)calculated for[C14H15BrSi]+requires m/z 290.0126,found m/z290.0130.
IV-10:(S)-1-(4-三氟甲基苯基)乙基苯硅烷
(S)-phenyl(1-(4-(trifluoromethyl)phenyl)ethyl)silane
油状液体，83％yield，[α]20 D＝-9.9(c 1.10,CHCl3),98.9％ee,IR(cm-1):2957,2927,2141,1616,1327,1120.1H NMR(CDCl3,400MHz):δ7.48(d,J＝8.0Hz,2H),7.44-7.35(m,3H),7.35-7.28(m,2H),7.16(d,J＝8.0Hz,2H),4.32(d,J＝2.8Hz,2H),2.75-2.64(m,1H),1.47(d,J＝7.2Hz,3H)；13C NMR:(CDCl3,100MHz):δ149.0,135.6,130.5,130.0,128.0,127.3,125.3,125.24,125.20,25.8,16.0；19F NMR:(376.5MHz,CDCl3)δ-62.2；HRMS(ESI)calculated for[C15H16F3Si]+(M+H+)requires m/z 281.0973,found m/z 281.0967.
IV-11:(S)-4-(1-苯硅基乙基)苯甲酸甲酯
(S)-methyl 4-(1-(phenylsilyl)ethyl)benzoate
油状液体，94％yield，[α]20 D＝-16.9(c 1.08,CHCl3),98.9％ee,IR(cm-1):2955,2925,2140,1724,1280.1H NMR(CDCl3,400MHz):δ7.97-7.87(m,2H),7.43-7.34(m,3H),7.34-7.27(m,2H),7.12(d,J＝8.0Hz,2H),4.32(d,J＝3.2Hz,2H),3.90(s,3H),2.76-2.64(m,1H),1.47(d,J＝7.2Hz,3H)；13C NMR:(CDCl3,100MHz):δ167.2,150.4,135.6,130.6,130.0,129.7,127.9,127.0,126.9,51.9,26.1,15.9；HRMS(ESI)calculated for[C16H19O2Si]+(M+H+)requires m/z 271.1154,found m/z 271.1163.
IV-12:(S)-4-(1-苯硅基乙基)乙酸苄酯
(S)-4-(1-(phenylsilyl)ethyl)benzyl acetate
油状液体，86％yield，[α]20 D＝-15.6(c 1.12,CHCl3),99.5％ee,IR(cm-1):2956,2924,2137,1741,1231.1H NMR(CDCl3,400MHz):δ7.46-7.36(m,3H),7.35-7.28(m,2H),7.24(d,J＝8.4Hz,2H),7.09(d,J＝8.0Hz,2H),5.06(s,2H),4.37-4.26(m,2H),2.69-2.57(m,1H),2.10(s,3H),1.44(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ170.8,144.8,135.5,132.5,131.1,129.7,128.5,127.8,127.2,66.1,25.1,20.9,16.3；HRMS(ESI)calculatedfor[C17H21O2Si]+(M+H+)requires m/z 285.1311,found m/z 285.1310.
IV-13:(S)-1-(4-(2-甲基-1,3-二氧环戊基-2-)苯基)乙基苯硅烷
(S)-(1-(4-(2-methyl-1,3-dioxolan-2-yl)phenyl)ethyl)(phenyl)silane
白色固体，94％yield，熔点:90-92℃.[α]20 D＝-14.3(c 0.97,CHCl3),99.0％ee,IR(cm-1):2955,2925,2136,1459,1374.1H NMR(CDCl3,400MHz):δ7.49-7.27(m,7H),7.07(d,J＝8.0Hz,2H),4.40-4.25(m,2H),4.13-3.95(m,2H),3.88-3.72(m,2H),2.70-2.55(m,1H),1.65(s,3H),1.44(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ144.1,135.6,131.3,129.7,127.8,126.8,125.3,108.8,64.4,27.5,25.0,16.3；HRMS(EI)calculated for[C18H22O2Si]+requires m/z 298.1389,found m/z 298.1389.
IV-14:(S)-1-(3-三氟甲基苯基)乙基苯硅烷
(S)-phenyl(1-(3-(trifluoromethyl)phenyl)ethyl)silane
油状液体，84％yield，[α]20 D＝-10.5(c 1.31,CHCl3),98.8％ee,IR(cm-1):2956,2926,2140,1447,1330.1H NMR(CDCl3,400MHz):δ7.44-7.21(m,9H),4.32(d,J＝2.8Hz,2H),2.74-2.63(m,1H),1.47(d,J＝7.2Hz,3H)；13C NMR:(CDCl3,100MHz):δ145.6,135.6,130.5,130.4,130.0,128.7,128.0,123.8,123.7,121.9,121.8,25.7,16.0；19F NMR:(376.5MHz,CDCl3)δ-62.6；HRMS(ESI)calculated for[C15H16F3Si]+(M+H+)requires m/z 281.0973,found m/z 281.0980.
IV-15:(S)-1-(3-氯苯基)乙基苯硅烷
(S)-(1-(3-chlorophenyl)ethyl)(phenyl)silane
油状液体，74％yield，[α]20 D＝-20.5(c 1.10,CHCl3),98.6％ee,IR(cm-1):2956,2140,1593,1476,1427.1H NMR(CDCl3,400MHz):δ7.45-7.36(m,3H),7.36-7.28(m,2H),7.16(dd,J＝7.6,7.6Hz,1H),7.12-7.02(m,2H),6.94(d,J＝7.6Hz,1H),4.31(d,J＝2.8Hz,2H),2.67-2.53(m,1H),1.43(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ146.8,135.6,134.2,130.7,129.9,129.5,127.9,127.1,125.3,125.2,25.4,16.1；HRMS(EI)calculated for[C14H15ClSi]+requires m/z 246.0632,found m/z 246.0634.
IV-16:(S)-1-间甲苯基乙基苯硅烷
(S)-Phenyl(1-(m-tolyl)ethyl)silane
油状液体，76％yield，[α]20 D＝-20.1(c 1.07,CHCl3),99.4％ee,IR(cm-1):2955,2924,2136,1604,1430.1H NMR(CDCl3,400MHz):δ7.44-7.35(m,3H),7.34-7.28(m,2H),7.17-7.11(m,1H),6.96-6.87(m,3H),4.34-4.28(m,2H),2.62-2.53(m,1H),2.29(s,3H),1.44(d,J＝7.4Hz,3H)；13C NMR:(CDCl3,100MHz):δ144.5,137.8,135.6,131.5,129.7,128.2,127.9,127.8,125.8,124.1,25.2,21.4,16.4.HRMS(EI)calculated for[C15H18Si]+requires m/z 226.1178,found m/z 226.1178.
IV-17:(S)-1-邻甲苯基乙基苯硅烷
(S)-Phenyl(1-(o-tolyl)ethyl)silane
油状液体，62％yield，[α]20 D＝+32.8(c 0.89,CHCl3),99.8％ee,IR(cm-1):3017,2955,2925,2136,1459.1H NMR(CDCl3,400MHz):δ7.43-7.36(m,3H),7.34-7.28(m,2H),7.19-7.13(m,1H),7.10(d,J＝7.6Hz,2H),7.07-7.01(m,1H),4.32-4.25(m,2H),2.82-2.73(m,1H),2.20(s,3H),1.45(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ142.8,135.6,134.8,131.6,130.1,129.7,127.8,126.2,126.0,124.8,20.8,20.0,16.6.HRMS(EI)calculated for[C15H18Si]+requires m/z 226.1178,found m/z 226.1181.
IV-18:(S)-1-(3-甲氧基-4-氟苯基)乙基苯硅烷
(S)-(1-(4-fluoro-3-methoxyphenyl)ethyl)(phenyl)silane
油状液体，87％yield，[α]20 D＝-18.3(c 1.07,CHCl3),99.4％ee,IR(cm-1):3069,2136,1607,1515,1416,1276.1H NMR(CDCl3,400MHz):δ7.48-7.36(m,3H),7.36-7.28(m,2H),6.94(dd,J＝8.4,11.2Hz,1H),6.66-6.52(m,2H),4.40-4.25(m,2H),3.74(s,3H),2.65-2.51(m,1H),1.44(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ150.2(d,J＝241.3Hz,1C),147.1(d,J＝10.9Hz,1C),140.7(d,J＝3.7Hz,1C),135.6,131.1,129.8,127.9,118.7(d,J＝6.5Hz,1C),115.7(d,J＝17.5Hz,1C),112.4,55.9,25.1,16.4；19F NMR:(376.5MHz,CDCl3)δ-140.6；HRMS(EI)calculated for[C15H17FOSi]+requires m/z260.1033,found m/z 260.1035.
IV-19:(S)-1-(萘基-1-)乙基苯硅烷
(S)-(1-(naphthalen-1-yl)ethyl)(phenyl)silane
油状液体，83％yield，[α]20 D＝+148(c 0.89,CHCl3),98.1％ee,IR(cm-1):2955,2924,2139,1510,1460.1H NMR(CDCl3,400MHz):δ8.10-8.02(m,1H),7.90-7.80(m,1H),7.66(d,J＝8.0Hz,1H),7.53-7.34(m,6H),7.33-7.21(m,3H),4.47-4.31(m,2H),3.50-3.39(m,1H),1.59(d,J＝7.2Hz,3H)；13C NMR:(CDCl3,100MHz):δ140.8,135.6,133.9,131.4,131.1,129.7,128.9,127.8,125.6,125.5,125.3,123.4,123.2,20.0,16.8；HRMS(ESI)calculatedfor[C18H19Si]+(M+H+)requires m/z 263.1256,found m/z 263.1255.
IV-20:(S)-1-(萘基-2-)乙基苯硅烷
(S)-(1-(Naphthalen-2-yl)ethyl)(phenyl)silane
白色固体，85％yield，熔点:56-58℃.[α]20 D＝-46.8(c 0.98,CHCl3),98.8％ee,IR(cm-1):2956,2923,2137,1598,1462.1H NMR(CDCl3,400MHz):δ7.82-7.69(m,3H),7.50(s,1H),7.46-7.35(m,5H),7.33-7.22(m,3H),4.41-4.33(m,2H),2.83-2.74(m,1H),1.55(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ142.2,135.7,133.8,131.6,131.3,129.8,127.9,127.8,127.6,127.3,126.7,125.9,124.8,124.5,25.7,16.4.HRMS(EI)calculatedfor[C18H18Si]+requires m/z 262.1178,found m/z 262.1182.
IV-21:(S)-1-甲基-5-(1-苯硅基乙基)-吲哚
(S)-1-Methyl-5-(1-(phenylsilyl)ethyl)-1H-indole
油状液体，68％yield，[α]20 D＝-38.0(c 0.50,CHCl3).99.2％ee,IR(cm-1):2953,2924,2868,2132,1513,1488.1H NMR(CDCl3,400MHz):δ7.47-7.43(m,2H),7.40-7.34(m,2H),7.33-7.27(m,2H),7.21(d,J＝8.4Hz,1H),7.03-6.98(m,2H),6.39(d,J＝3.2Hz,1H),4.38-4.32(m,2H),3.76(s,3H),2.74-2.66(m,1H),1.50(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ135.6,135.3,135.0,132.1,129.5,128.8,127.8,121.7,118.5,109.0,100.4,32.7,24.9,17.4.HRMS(EI)calculated for[C17H19NSi]+requires m/z 265.1287,found m/z 265.1290.
IV-22:(S)-1-(噻吩基-2-)乙基苯硅烷
(S)-Phenyl(1-(thiophen-2-yl)ethyl)silane
油状液体，77％yield，[α]20 D＝-4.6(c 1.21,toluene),98.0％ee,IR(cm-1):2956,2925,2867,2140,1457,1431.1H NMR:(CDCl3,400MHz)δ7.48-7.43(m,2H),7.41-7.37(m,1H),7.36-7.29(m,2H),7.05(dd,J＝5.0,1.0Hz,1H),6.90(dd,J＝5.2,3.6Hz,1H),6.71-6.65(m,1H),4.45-4.35(m,2H),2.95-2.85(m,1H),1.49(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ148.4,135.6,130.9,129.9,127.9,126.8,122.3,121.9,20.7,18.0.HRMS(EI)calculated for[C12H14SSi]+requires m/z 218.0585,found m/z 218.0585.
IV-23:(S)-1-(苯并噻吩基-3-)乙基苯硅烷
(S)-(1-(benzo[b]thiophen-3-yl)ethyl)(phenyl)silane
油状液体，72％yield，[α]20 D＝+150.6(c 1.07,CHCl3),98.5％ee,IR(cm-1):2955,2924,2868,2140,1458,1428.1H NMR(CDCl3,400MHz):δ7.89-7.82(m,1H),7.76-7.69(m,1H),7.45-7.27(m,7H),6.89(s,1H),4.46-4.32(m,2H),3.07-2.96(m,1H),1.54(d,J＝7.2Hz,3H)；13C NMR:(CDCl3,100MHz):δ140.4,139.1,138.3,135.7,131.0,129.8,127.9,124.2,123.6,122.8,121.9,119.0,18.7,16.3；HRMS(ESI)calculated for[C16H16SSiNa]+(M+Na+)requires m/z 291.0640,found m/z 291.0644.
IV-24:(S)-2-甲氧基-5-(1-(苯硅基)乙基)吡啶
(S)-2-methoxy-5-(1-(phenylsilyl)ethyl)pyridine
油状液体，74％yield，[α]20 D＝-12.2(c 1.20,CHCl3),99.0％ee,IR(cm-1):2925,2869,2136,1604,1491.1H NMR(CDCl3,400MHz):δ7.90(d,J＝2.4Hz,1H),7.45-7.36(m,3H),7.35-7.24(m,3H),6.64(d,J＝8.4Hz,1H),4.32(d,J＝3.2Hz,2H),3.90(s,3H),2.59-2.49(m,1H),1.43(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ162.1,144.7,137.4,135.4,132.3,130.6,129.8,127.9,110.3,53.0,21.4,16.4；HRMS(EI)calculated for[C14H17NOSi]+requires m/z 243.1079,found m/z 243.1077.
IV-25:(S)-(正辛基-2-)苯硅烷
(S)-Octan-2-yl(phenyl)silane
油状液体，91％yield，[α]20 D＝+5.8(c 1.06,CHCl3).84.9％ee,IR(cm-1):2956,2924,2855,2131,1462,1430.1H NMR(CDCl3,400MHz):δ7.56(dd,J＝1.6,7.6Hz,2H),7.42-7.32(m,3H),4.25-4.16(m,2H),1.52-1.38(m,2H),1.35-1.20(m,8H),1.18-1.09(m,1H),1.05(d,J＝6.6Hz,3H),0.87(t,J＝6.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ135.6,132.3,129.4,127.9,33.5,31.8,29.4,28.5,22.7,16.3,16.1,14.1.HRMS(EI)calculated for[C14H24Si]+requires m/z 220.1647,found m/z 220.1646.
IV-26:(S)-((5-溴正戊基)-2-)苯硅烷
(S)-(5-bromopentan-2-yl)(phenyl)silane
油状液体，53％yield，[α]20 D＝+2.6(c 1.13,toluene),84.7％ee,IR(cm-1):2925,2853,2133,1460,1377.1H NMR(CDCl3,400MHz):δ7.62-7.51(m,2H),7.47-7.31(m,3H),4.35-4.12(m,2H),3.49-3.25(m,2H),2.10-1.80(m,2H),1.73-1.59(m,1H),1.52-1.38(m,1H),1.24-1.00(m,4H)；13C NMR:(CDCl3,100MHz):δ135.6,131.5,129.6,127.9,33.6,31.9,31.7,15.9,15.6；HRMS(ESI)calculated for[C11H18BrSi]+(M+H+)requires m/z 257.0361,found m/z 257.0362.
IV-27:(S)-2-(10-(苯硅基)十一烷基)异吲哚-1,3-二酮
(S)-2-(10-(phenylsilyl)undecyl)isoindoline-1,3-dione
油状液体，89％yield，Optical Rotation:[α]20 D＝+2.9(c 0.78,CHCl3),80.8％ee,IR(cm-1):2925,2854,2129,1715,1396.1H NMR(CDCl3,400MHz):δ7.84(dd,J＝3.2,5.2Hz,2H),7.70(dd,J＝2.8,5.2Hz,2H),7.61-7.50(m,2H),7.43-7.30(m,3H),4.30-4.10(m,2H),3.67(t,J＝7.2Hz,2H),1.77-1.60(m,2H),1.45-1.17(m,14H),1.17-1.00(m,4H)；13C NMR:(CDCl3,100MHz):δ168.3,135.5,133.7,132.14,132.11,129.3,127.8,123.0,38.0,33.4,29.5,29.4,29.1,28.5,28.4,26.8,16.2,16.1；HRMS(EI)calculated for[C25H33NO2Si]+requires m/z 407.2281,found m/z 407.2280.
IV-28：(S)-5-苯硅基己基-1-醇
(S)-5-(phenylsilyl)hexan-1-ol
油状液体，77％yield，Optical Rotation:[α]20 D＝+4.7(c 1.24,CHCl3),81.3％ee,IR(cm-1):3359,2926,2862,2128,1459,1429.1H NMR(CDCl3,400MHz):δ7.56(d,J＝7.6Hz,2H),7.43-7.31(m,3H),4.26-4.17(m,2H),3.61(t,J＝6.4Hz,2H),1.64-1.46(m,4H),1.42-1.31(m,2H),1.28-1.20(m,1H),1.20-1.10(m,1H),1.07(d,J＝6.8Hz,3H)；13CNMR:(CDCl3,100MHz):δ135.5,131.9,129.4,127.8,77.3,77.0,76.7,62.6,33.1,32.6,24.6,16.2,16.0；HRMS(EI)calculated for[C12H20OSi–H2]+requires m/z 206.1127,foundm/z 206.1125.
IV-29：(S)-5-苯硅基己基-2-酮
(S)-5-(phenylsilyl)hexan-2-one
油状液体，81％yield，Optical Rotation:[α]20 D＝+4.2(c 1.10,CHCl3),82.6％ee,IR(cm-1):2924,2866,2130,1716,1458,1429.1H NMR(CDCl3,400MHz):δ7.59-7.53(m,2H),7.44-7.33(m,3H),4.27-4.18(m,2H),2.60-2.39(m,2H),2.10(s,3H),1.87-1.76(m,1H),1.67-1.54(m,1H),1.20-1.09(m,1H),1.07(d,J＝6.8Hz,3H)；
13C NMR:(CDCl3,100MHz):δ208.4,135.4,131.2,129.5,127.8,77.3,77.0,76.7,42.3,29.6,27.1,15.7,15.6；HRMS(EI)calculated for[C12H18OSi]+requires m/z206.1127,found m/z 206.1129.
IV-30:(S)-(对甲氧基苯基)(1-苯基乙基)硅烷
(S)-(4-Methoxyphenyl)(1-phenylethyl)silane
油状液体，97％yield，[α]20 D＝-16.1(c 1.04,CHCl3),99.5％ee,IR(cm-1):2955,2924,2134,1596,1377,1115.1H NMR(CDCl3,400MHz):δ7.31(d,J＝8.4Hz,2H),7.27-7.21(m,2H),7.14-7.06(m,3H),6.85(d,J＝8.4Hz,2H),4.30(d,J＝3.2Hz,2H),3.80(s,3H),2.62-2.53(m,1H),1.44(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ161.0,144.7,137.2,128.3,127.1,124.9,122.0,113.7,55.0,25.6,16.3.HRMS(EI)calculated for[C15H18OSi]+requires m/z 242.1127,found m/z 242.1126.
IV-31:(S)-(对氯苯基)(1-苯基乙基)硅烷
(S)-(4-Chlorophenyl)(1-phenylethyl)silane
油状液体，80％yield，[α]20 D＝-19.3(c 0.95,CHCl3),99.4％ee,IR(cm-1):2956,2924,2855,2141,1580,1461.1H NMR(CDCl3,400MHz):δ7.31-7.21(m,6H),7.15-7.10(m,1H),7.06(d,J＝7.6Hz,2H),4.31(d,J＝3.2Hz,2H),2.64-2.55(m,1H),1.44(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ144.1,136.9,136.2,129.6,128.4,128.1,127.1,125.2,25.3,16.2.HRMS(EI)calculated for[C14H15ClSi]+requires m/z 246.0632,found m/z246.0632.
实施例2：产物氧化合成手性醇类化合物(应用实例)
20mL反应管中，加入1a(0.087g,0.3mmol)、二氯甲烷(15mL)，0℃下搅拌并加入HBF4·Et2O(0.35g,1.6mmol,40％Wt).搅拌3h，旋去溶剂，然后按顺序加入四氢呋喃(3mL),甲醇(3mL),氟化钾(0.07g,1.2mmol),碳酸氢钾(0.30g,3.0mmol),H2O2(1.5mL,30％wt).室温搅拌15h,加水稀释，乙醚萃取3次，饱和食盐水洗涤，无水硫酸钠干燥，旋干，PE/EtOAc＝4/1过柱得到0.048g(0.24mmol,81％yield)目标产物。白色固体,[α]20 D＝-42(c 0.27,CHCl3),99％ee,1H NMR(CDCl3,400MHz):δ7.55-7.61(m,4H),7.40-7.47(m,4H),7.31-7.37(m,1H),4.95(q,J＝6.4Hz,1H),1.86(br,1H),1.54(d,J＝6.4Hz,3H).(实验步骤参考文献：Bergens,S.H.；Noheda,P.；Whelan,J.；Bosnich,B.J.Am.Chem.Soc.1992,114,2121-2128.化合物数据与文献一致：Salvi,N.A.；Chattopadhyay,S.Tetrahedron.2001,57,2833–2839.)
取实施例1的合成产物参照上述方法氧化成手性醇类化合物，结果如下表1所示：
表1
实施例3：产物氧化合成硅醇类化合物(应用实例)
20mL反应管中加入2a(0.1046g,0.5mmol),BCl3(0.5mmol,0.5mL,1.0M inDCM),H2O(1.2mL)、二氯甲烷(2.0mL).搅拌过夜,加水稀释，二氯甲烷萃取3次，饱和食盐水洗涤，无水硫酸钠干燥。PE/EtOAc＝10/1过柱得到0.0790g(0.35mmol,70％yield)目标产物。油状液体，1:1dr.1H NMR(CDCl3,400MHz):δ7.45-7.51(m,2H),7.19-7.44(m,12H),7.03-7.15(m,6H),4.93(d,J＝1.8Hz,1H),4.90(d,J＝2.4Hz,1H),2.48-2.57(m,2H),2.17(br,2H),1.41(d,J＝7.8Hz,3H),1.38(d,J＝7.8Hz,3H).(化合物数据与文献一致：Visco,M.D.；Wieting,J.M.；Mattson,A.E.Org.Lett.2016,18,2883-2885.)
实施例4：产物氧化合成手性硅醇类化合物(应用实例)
20mL反应管中加入3a(0.13g,0.62mmol),Pd/C(0.062g,0.06mmol),H2O(0.2mL)、Et2O(2.0mL)。搅拌过夜，过滤，滤液加水稀释，乙醚萃取3次，饱和食盐水洗涤，无水硫酸钠干燥。PE/EtOAc＝1/1过柱得到0.14g(0.57mmol,92％yield)目标产物。白色固体.熔点:120-122℃.[α]20 D＝-17.0(c 0.44,CHCl3),99％ee,IR(cm-1):3315,1597,1491,1455,1430,1379,1123.1H NMR(CDCl3,400MHz):δ7.55(d,J＝7.6Hz,2H),7.39-7.47(m,1H),7.35(t,J＝7.6Hz,2H),7.20-7.29(m,2H),7.08-7.18(m,3H),2.79(br,2H),2.49(q,J＝7.6Hz,1H),1.41(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ143.3,134.3,133.4,130.4,128.5,127.8,127.5,125.1,28.9,14.5.HRMS(EI)calculated for[C14H16O2Si]+requires m/z244.0920,found m/z 244.0918.(实验步骤参考文献：Visco,M.D.；Wieting,J.M.；Mattson,A.E.Org.Lett.2016,18,2883-2885.)
20mL反应管中加入4a(0.16g,0.69mmol),Pd/C(0.073g,0.068mmol),H2O(0.2mL)、Et2O(2.0mL)。搅拌过夜，过滤，滤液加水稀释，乙醚萃取3次，饱和食盐水洗涤，无水硫酸钠干燥。PE/EtOAc＝1/1过柱得到0.12g(0.46mmol,67％yield)目标产物。白色固体.熔点:111-113℃.[α]20 D＝-13.0(c 0.94,CHCl3),99％ee,IR(cm-1):3337,2958,2922,1599,1508.1H NMR(CDCl3,400MHz):δ7.57-7.50(m,2H),7.47-7.40(m,1H),7.39-7.32(m,2H),7.12-7.04(m,2H),6.98-6.90(m,2H),2.53-2.43(m,3H),1.41(d,J＝7.6Hz,3H)；13C NMR:(CDCl3,100MHz):δ162.8,138.8,134.3,133.1,130.5,128.8,127.8,115.0,28.0,14.7；19FNMR:(376.5MHz,CDCl3)δ-118.6；HRMS(EI)calculated for[C14H15FO2Si]+requires m/z262.0825,found m/z 262.0827.(实验步骤参考文献：Visco,M.D.；Wieting,J.M.；Mattson,A.E.Org.Lett.2016,18,2883-2885.)
20mL反应管中加入5a(0.17g,0.77mmol),Pd/C(0.086g,0.081mmol),H2O(0.2mL)、Et2O(2.0mL)。搅拌过夜，过滤，滤液加水稀释，乙醚萃取3次，饱和食盐水洗涤，无水硫酸钠干燥。PE/EtOAc＝1/1过柱得到0.13g(0.53mmol,69％yield)目标产物。白色固体.熔点:52-54℃.[α]20 D＝-6.4(c 1.18,CHCl3),85％ee,IR(cm-1):3351,2956,2924,2854,1462,1378.1H NMR(CDCl3,400MHz):δ7.68-7.60(m,2H),7.48-7.32(m,3H),2.83-2.54(m,2H),1.66-1.51(m,1H),1.49-1.35(m,1H),1.33-1.13(m,8H),1.02(s,4H),0.86(t,J＝6.8Hz,3H)；13C NMR:(CDCl3,100MHz):δ134.5,134.2,130.0,127.7,31.9,30.6,29.3,28.3,22.7,19.1,14.1,13.2；HRMS(EI)calculated for[C14H24O2Si-C6H6]+requires m/z 174.1076,found m/z 174.1078.(实验步骤参考文献：Visco,M.D.；Wieting,J.M.；Mattson,A.E.Org.Lett.2016,18,2883-2885.)
实施例5：产物合成多取代硅烷化合物(应用实例)
干燥的20mL的反应管中，加入苯乙烯(63μL,0.5mmol),6a(0.0682g,0.32mmol),iPrOIP-FeCl2(0.0133g,0.025mmol),NaBHEt3(75μL,0.075mmol),反应12小时,PE/EtOAc(50:1―20:1)过柱得到0.0795g(0.25mmol,78％yield,2.7:1dr)。目标产物，油状液体.IR(cm-1):3024,2925,2114,1600,1492,1452.1H NMR(400MHz,CDCl3):δ7.48-7.41(m,1.51H),7.41-7.28(m,3.51H),7.26-7.16(m,4H),7.15-7.00(m,5.57H),7.00-6.95(m,0.57H),4.35-4.30(m,0.28H),4.30-4.23(m,0.72H),2.63-2.39(m,3H),1.40(d,J＝7.6Hz,0.84H),1.37(d,J＝7.6Hz,2.20H),1.22-1.14(m,0.59H),1.14-1.05(m,1.49H)；HRMS(EI)calculated for[C22H24Si]+requires m/z 316.1647,found m/z 316.1647.(实验步骤参考文献：Chen,J.H.；Cheng,B.；Cao,M.Y.；Lu,Z.Angew.Chem.Int.Ed.2015,54,4661–4664.)
实施例6：产物合成多取代硅烷化合物(应用实例)
干燥的20mL的反应管中，加入苯乙炔(110μL,1.0mmol),7a(0.11g,0.53mmol),Xantphos-CoBr2(Xantphos与CoBr2形成的金属络合物)(0.041g,0.052mmol),NaBHEt3(150μL,0.15mmol),反应5小时,PE过柱得到0.097g(0.31mmol,59％yield,2.7:1dr)目标产物，油状液体.IR(cm-1):2955,2925,2119,1600,1493.1H NMR(CDCl3,400MHz):δ7.50-7.26(m,10H),7.24-7.17(m,2H),7.15-7.03(m,3H),7.02-6.98(m,0.36H),6.92(d,J＝19.2Hz,0.70H),6.53(dd,J＝3.6,18.8Hz,0.26H),6.38(dd,J＝3.6,19.2Hz,0.69H),4.62(dd,J＝2.8,3.2Hz,1.0H),2.73-2.61(m,1H),1.51-1.42(m,3H)；HRMS(EI)calculated for[C22H22Si]+requires m/z 314.1491,found m/z 314.1487.(实验步骤参考文献：Guo,J.；Lu,Z.Angew.Chem.Int.Ed.2016,55,10835-10838.)
实施例7：产物合成多取代硅烷化合物(应用实例)
干燥的20mL的反应管中，加入苯乙炔(66μL,0.6mmol),8a(0.11g,0.53mmol),2,4-DMBOIP·CoBr2(0.015g,0.025mmol),NaBHEt3(75μL,0.075mmol),反应3小时,PE过柱得到0.10g(0.33mmol,63％yield,2.7:1dr)目标产物，油状液体.IR(cm-1):2956,2925,2125,1599,1492.1H NMR(CDCl3,400MHz,):δ7.57-7.27(m,6H),7.24-6.95(m,9H),6.17(d,J＝2.0Hz,0.25H),6.01(d,J＝2.4Hz,0.69H),5.75(d,J＝2.4Hz,0.25H),5.65(d,J＝2.4Hz,0.69H),4.77(d,J＝3.6Hz,1H),2.73-2.63(m,1H),1.44(d,J＝7.6Hz,0.85H),1.39(d,J＝7.6Hz,2.13H)；HRMS(EI)calculated for[C22H22Si]+requires m/z 314.1491,found m/z314.1494.(实验步骤参考文献：Guo,J.；Lu,Z.Angew.Chem.Int.Ed.2016,55,10835-10838.)
实施例8不同催化剂催化效率和选择性
室温下，氮气保护下，在一干燥的反应试管中加入手性CoX2-OIP络合物(0.05mmol)，苯乙烯(1.2mmol)，苯基硅烷(1.0mmol)，THF(4mL)，叔丁醇钠(0.15mmol)，然后在室温搅拌1小时后停止反应，通过均三甲苯作内标计算1和2的核磁产率，通过高效液相色谱测1的ee值。反应式中，1为手性产物，2为非手性副产物，不同催化剂的选择性如下。手性CoX2-OIP络合物催化剂和产物情况如下表2所示
表2
| Entry | R9 | R11 | R13 | R8 | NMR yield of 1 | NMR yield of 2 | Eeof 1 |
| 1 | Me | H | Me | iPr | 69 | 3.6 | 72.2 |
| 2 | iPr | H | iPr | iPr | 69 | 5.4 | 88.2 |
| 3 | -CHPh2 | Me | -CHPh2 | iPr | 59 | 3.9 | 98.6 |
| 4 | -CHPh2 | Cl | -CHPh2 | iPr | 54 | 1.6 | 98.8 |
| 5 | -CHPh2 | -OMe | -CHPh2 | iPr | 63 | 2.8 | 98.7 |
| 6 | -CHPh2 | -OMe | -CHPh2 | Bn | 70 | 1.2 | 98.5 |
| 7 | -CHPh2 | -OMe | -CHPh2 | tBu | 6.3 | 12 | -- |
| 8 | -CHPh2 | -OMe | -CHPh2 | Me | 74 | 1.2 | 97.9 |
从表2可以看出，催化剂6的目标手性产物收率最高，非手性副产物收率最低，因此选用催化剂6为最优催化剂，实施例1均以催化剂6进行合成。
催化剂参照参考文献：Guo,J.；Shen,X.Z.；Lu,Z.Angew.Chem.Int.Ed.2017,56,615-618.合成，催化剂1、2为已公开化合物，催化剂3-8的产物分析数据如下：
催化剂3
绿色粉末.Anal.Calcd for C46H43Cl2CoN3O+1.5H2O:C,68.15；H,5.72；N,5.18；Found:C,68.37；H,5.56；N,5.09.
催化剂5
绿色粉末.Anal.Calcd for C46H43Cl2CoN3O2+2H2O:C,66.11；H,5.67；N,5.03；Found:C,66.35；H,5.39；N,5.39.
催化剂4
绿色粉末.Anal.Calcd for C45H40Cl3CoN3O+2H2O:C,64.33；H,5.28；N,5.00；Found:C,64.49；H,5.06；N,4.90.
催化剂8
棕色粉末.Anal.Calcd for C44H39Cl2CoN3O2+2H2O:C,65.43；H,5.37；N,5.20；Found:C,65.67；H,5.14；N,5.14.
催化剂7
绿色粉末.Anal.Calcd for C47H45Cl2CoN3O2+2H2O:C,66.43；H,5.81；N,4.95；Found:C,66.53；H,5.72；N,4.72.
Claims (10)
1.一种手性二氢硅烷化合物，所述手性二氢硅烷化合物如式IV所示：
式IV中，*代表手性碳原子；
R1,R2任选自C1-C16的烷基、C3-C16的环烷基、苄基、萘基、邻苯二甲酰亚胺基、式V所示的基团或C4～C10的含N、O、S的杂环芳基A；所述烷基、环烷基上的H不被取代或被1个以上的取代基A取代，所述取代基A包括硝基、卤素、苯基、邻苯二甲酰亚胺基、杂环芳基B、甲氧羰基、羰基、三氟甲基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；所述杂环芳基B包括吲哚基、噻吩基、吡啶基或喹啉基；所述苄基、萘基、含N、O、S的杂环芳基A上的H不被取代或被1个以上的取代基B取代，所述取代基B包括C1～C3的烷基、C1～C3的烷氧基、硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基或邻苯二甲酰亚胺基；所述含N、O、S的杂环芳基A包括噻吩基、苯并噻吩基、吲哚基、N-甲基吲哚基、吡啶基、喹啉基或呋喃基；
式V中，R3、R4、R5、R6、R7任选自H、卤素、C1-C16的烷基、C1-C16的烷氧基、C1-C16的烷硫基、苯基、三氟甲基、甲氧羰基、硝基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基、乙酰氧甲基、2-甲基-1,3-二氧环戊基中的任意一种。
2.如权利要求1所述的手性二氢硅烷化合物，其特征在于所述R1为C1-C10的烷基、萘基、N-甲基吲哚基、噻吩基、苯并噻吩基、吡啶基、2-甲氧基吡啶基或式V所示的基团；所述烷基的H不被取代或被1个以上的取代基A取代，所述取代基A为硝基、卤素、苯基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、邻苯二甲酰亚胺基、吲哚基、噻吩基或吡啶基；
R2为式V所示的基团；
式V所示的基团为苯基或含有1～2个以下取代基的取代苯基：甲基、丁基、苯基、甲氧基、甲硫基、F、Cl、Br、三氟甲基、甲氧羰基、乙酰氧甲基、2-甲基-1,3-二氧环戊基。
3.如权利要求1所述的手性二氢硅烷化合物，其特征在于所述R1为苯基、对甲基苯基、对丁基苯基、联苯基、对甲氧基苯基、对甲硫基苯基、对氟苯基、对氯苯基、对溴苯基、对三氟甲基苯基、对甲氧羰基苯基、对乙酰氧甲基苯基、4-(2-甲基-1,3-二氧环戊基)苯基、间三氟甲基苯基、间氯苯基、间甲基苯基、邻甲基苯基、3-甲氧基-4-氟苯基、1-萘基、2-萘基、N-甲基吲哚基、噻吩基、苯并噻吩基、2-甲氧基吡啶基、CH3(CO)CH2CH2-、正己基、溴代丙基、1-羟基-丁基或异吲哚-1,3-二酮取代的壬基；
R2为苯基、对甲氧基苯基或对氯苯基。
4.如权利要求1～3之一所述的手性二氢硅烷化合物的合成方法，其特征在于所述方法为：以式I所示的烯烃和式II所示的硅烷为原料，手性CoX2-OIP络合物为催化剂，在还原剂存在下，反应制得式IV所示的手性二氢硅烷化合物；
R2SiH3 II
所述手性CoX2-OIP络合物为式III所示的化合物或其对映体；
式III中，R8，R9,R10,R11,R12,R13,R14,R15,R16,R17,R18,R19任选自H、C1-C16的烷基、C1-C16的烷氧基、卤素、苯基、萘基或苄基：所述烷基、烷氧基上的H不被取代或被1个以上的取代基C取代，所述取代基C包括硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；
所述苯基、苄基、萘基上的H不被取代或被1个以上的取代基D取代，所述取代基D包括C1～C3的烷基、C1～C3的烷氧基、硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、羰基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；
X为F、Cl、Br、I、OAc、CF3SO3中的任意一种。
5.如权利要求4所述的方法，其特征在于所述手性CoX2-OIP络合物催化剂为式III所示的化合物，式III中，R8为C1-C4的烷基或苄基、R9为C1-C4的烷基或二苯基次甲基，R10为H，R11为C1-C4的烷基、C1-C4的烷氧基或卤素；R12为H；R13为C1-C4的烷基或二苯基次甲基；R14为甲基；R15、R16、R17、R18、R19均为H，X为Cl。
6.如权利要求4所述的方法，其特征在于所述手性CoX2-OIP络合物催化剂如式III-1所示
7.如权利要求4～6之一所述的方法，其特征在于所述的式II所示的硅烷、式I所示的烯烃、手性CoX2-OIP络合物、还原剂的物质的量之比为1：0.1-10：0.0000005-0.05：0.0000005-0.15。
8.如权利要求4～6之一所述的方法，其特征在于所述方法在无溶剂条件或在有机溶剂中进行，在有机溶剂中反应时，所述的有机溶剂为苯、四氯化碳、甲苯、四氢呋喃、乙醚、二氯甲烷、乙腈、二氧六环、石油醚、环己烷、正己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中的任意一种。
9.如权利要求1所述的手性二氢硅烷化合物在合成手性醇类化合物、手性硅醇类化合物、手性多取代硅烷类化合物中的应用。
10.如权利要求5所述的合成方法中的用于合成手性二氢硅烷化合物的手性CoX2-OIP络合物催化剂，所述手性CoX2-OIP络合物催化剂为式III所示的化合物，式III中，R8为C1-C4的烷基或苄基、R9为C1-C4的烷基或二苯基次甲基，R10为H，R11为C1-C4的烷基、C1-C4的烷氧基或卤素；R12为H；R13为C1-C4的烷基或二苯基次甲基；R14为甲基；R15、R16、R17、R18、R19均为H，X为Cl。
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