CN113943318A - Synthesis method of chiral phenyl silanol and 1, 2-chiral disilicon compound - Google Patents
Synthesis method of chiral phenyl silanol and 1, 2-chiral disilicon compound Download PDFInfo
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- CN113943318A CN113943318A CN202111222592.8A CN202111222592A CN113943318A CN 113943318 A CN113943318 A CN 113943318A CN 202111222592 A CN202111222592 A CN 202111222592A CN 113943318 A CN113943318 A CN 113943318A
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- -1 disilicon compound Chemical class 0.000 title claims abstract description 38
- YBRNUJSXEIBYFU-UHFFFAOYSA-N hydroxy(phenyl)silane Chemical compound O[SiH2]C1=CC=CC=C1 YBRNUJSXEIBYFU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 19
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 18
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 28
- BAFPRRDEEGCXRK-UHFFFAOYSA-N [SiH3]C=CC1=CC=CC=C1 Chemical compound [SiH3]C=CC1=CC=CC=C1 BAFPRRDEEGCXRK-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000000460 chlorine Chemical group 0.000 claims description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 6
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FIONWRDVKJFHRC-UHFFFAOYSA-N trimethyl(2-phenylethenyl)silane Chemical compound C[Si](C)(C)C=CC1=CC=CC=C1 FIONWRDVKJFHRC-UHFFFAOYSA-N 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 5
- PUQFRPWTZSYVOM-UHFFFAOYSA-N triethyl(2-phenylethenyl)silane Chemical compound CC[Si](CC)(CC)C=CC1=CC=CC=C1 PUQFRPWTZSYVOM-UHFFFAOYSA-N 0.000 claims description 5
- NXLACVVNHYIYJN-UHFFFAOYSA-N 1-phenyl-n-(1-phenylethyl)ethanamine Chemical compound C=1C=CC=CC=1C(C)NC(C)C1=CC=CC=C1 NXLACVVNHYIYJN-UHFFFAOYSA-N 0.000 claims description 4
- CSKRBHOAJUMOKJ-UHFFFAOYSA-N 3,4-diacetylhexane-2,5-dione Chemical compound CC(=O)C(C(C)=O)C(C(C)=O)C(C)=O CSKRBHOAJUMOKJ-UHFFFAOYSA-N 0.000 claims description 4
- HXVMIUKBXYWGNM-UHFFFAOYSA-N CCP(CC)CC.CCP(CC)CC.Cl.Cl Chemical compound CCP(CC)CC.CCP(CC)CC.Cl.Cl HXVMIUKBXYWGNM-UHFFFAOYSA-N 0.000 claims description 4
- FLUIQWLNRGHUIL-UHFFFAOYSA-N COC1=CC=CC=C1C1=CC=CC=C1OC.C(C)(C)(C)C=1C=C(C=C(C1)C(C)(C)C)PC1=CC(=CC(=C1)C(C)(C)C)C(C)(C)C Chemical group COC1=CC=CC=C1C1=CC=CC=C1OC.C(C)(C)(C)C=1C=C(C=C(C1)C(C)(C)C)PC1=CC(=CC(=C1)C(C)(C)C)C(C)(C)C FLUIQWLNRGHUIL-UHFFFAOYSA-N 0.000 claims description 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- SSAMRVVJWYZIDL-UHFFFAOYSA-N O1POC(C=C1)N Chemical compound O1POC(C=C1)N SSAMRVVJWYZIDL-UHFFFAOYSA-N 0.000 claims description 4
- KRWTWSSMURUMDE-UHFFFAOYSA-N [1-(2-methoxynaphthalen-1-yl)naphthalen-2-yl]-diphenylphosphane Chemical group COC1=CC=C2C=CC=CC2=C1C(C1=CC=CC=C1C=C1)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KRWTWSSMURUMDE-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052801 chlorine Chemical group 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000005311 nuclear magnetism Effects 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 150000008300 phosphoramidites Chemical class 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000007818 Grignard reagent Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 238000012827 research and development Methods 0.000 abstract 1
- 239000002210 silicon-based material Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QKGYJVXSKCDGOK-UHFFFAOYSA-N hexane;propan-2-ol Chemical compound CC(C)O.CCCCCC QKGYJVXSKCDGOK-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical class [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- 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
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- 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
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0832—Other preparations
-
- 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
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a method for synthesizing chiral phenyl silanol and a 1, 2-chiral disilicon compound by taking a strategy of carrying out asymmetric hydrosilation reaction on beta-silicon-based styrene and trichlorosilane under the catalysis of metal palladium; in the synthesis reaction of the chiral silicon-containing compound, the reaction condition is mild, the reaction efficiency is high, the substrate range is wide, the ee value of the standard substrate product is up to 98%, and the yield is 95%. The chiral silicon compound has very important application value in the fields of synthetic chemistry, material science, pharmaceutical chemistry, life science and the like. The chiral phenyl silanol compound and the 1, 2-chiral disilicon compound prepared by the method have good application prospects in the fields of organic synthesis, drug research and development and the like.
Description
Technical Field
The invention relates to the field of organic synthetic chemistry, in particular to a method for synthesizing chiral phenyl silanol and a 1, 2-chiral disilicon compound.
Background
The chiral silicon compound has very important application value in the fields of synthetic chemistry, material science, pharmaceutical chemistry, life science and the like. Therefore, it is important to develop a general and efficient method for synthesizing chiral silicon compounds with various structures.
The preparation of the chiral silicon compound with high regioselectivity and high stereoselectivity can be realized by the asymmetric hydrosilylation reaction of the olefin catalyzed by the transition metal, but the research on the synthesis of the 1, 2-chiral double silicon compound is less at present, and particularly the research on the method for performing the asymmetric hydrosilylation reaction by taking the olefin with silicon-based heteroatom introduced at the end of the double bond of the styrene as a substrate is less. The problem to be solved by the invention is how to efficiently obtain the 1, 2-chiral disilicon compound and the chiral phenyl silanol by taking the 1, 2-silicon-based substituted olefin as a substrate through asymmetric hydrosilylation.
Disclosure of Invention
In order to solve the problems, the invention provides a method for synthesizing chiral phenyl silanol and a 1, 2-chiral disilicon compound. The invention is realized by the following technical scheme:
a method for synthesizing chiral phenyl silanol comprises the following steps: under the catalytic condition of a transition metal palladium compound, carrying out asymmetric hydrosilation reaction on beta-silyl styrene and trichlorosilane, and then obtaining a chiral phenyl silanol compound under the condition of Fleming oxidation; the reaction equation is as follows:
wherein R is hydrogen or methyl or chlorine, [ Si ] is trimethyl silicon or triethyl silicon;
the asymmetric hydrosilation reaction is as follows: stirring 176mg of beta-silyl styrene, trichlorosilane, a transition metal palladium compound and a chiral phosphine ligand at low temperature under the protection of nitrogen, reacting for 12-48 hours, and performing the next step after nuclear magnetism monitoring till the reaction is complete.
Preferably, the synthesis method of the chiral phenyl silanol comprises the following steps:
s1.1, dissolving a product of asymmetric hydrosilylation in 4 mL/4 mL of methanol/tetrahydrofuran;
s1.2 KF (348.5mg,6 m) was added sequentially at-10-50 deg.Cmol)、KHCO3(600.7mg,6mmol)、30％H2O24 mL；
S1.3, heating the system to 40-100 ℃, and carrying out reflux reaction for 20-100 min;
s1.4 with saturated Na2S2O3Quenching the reaction with 5mL of solution;
s1.5, extracting the reaction solution by using methyl tert-butyl ether, wherein the dosage of each reaction solution is 5 milliliters, and the extraction is carried out for 3 times;
s1.6 combining the extracts in S1.5, and washing with saturated NaCl solution for 2 times, 10 ml of saturated saline solution each time;
s1.7 passing the organic phase over anhydrous Na2SO4Drying, concentrating, separating by glass column silica gel column chromatography, and purifying to obtain chiral phenyl silanol compound.
Preferably, in the method for synthesizing chiral phenyl silanol, the transition metal palladium compound is: [ PdCl (C)3H5)]2One or a combination of more of palladium acetate, palladium tetrakis (triphenylphosphine), palladium bis (triethylphosphine) dichloride and palladium bis (acetylacetone).
Preferably, in the above method for synthesizing chiral phenyl silanol, the chiral phosphine ligand is: (S) - (-) -2,2 '-bis [ bis (3, 5-di-tert-butylphenyl) phosphine ] -6,6' -dimethoxy-1, 1 '-biphenyl, (11BS) -N, N-bis (1-methylethyl) dinaphtho [2,1-D:1',2'-F ] [1,3,2] dioxaphosphin-4-amine, S- (-) -2,2' -bis (diphenylphosphino) -1,1 '-binaphthyl, (R) - (+) -2-diphenylphosphino-2' -methoxy-1, 1 '-binaphthyl, N-bis [ (R) -1-phenylethyl ] - [ (S) -1,1' -spiroindan-7, 7 '-diyl phosphoramidite, (R, S, S) - (3, 5-dioxa-4-phospha cyclohepta [2,1-a:3,4-a' ] dinaphthalen-4-yl) di (1-phenylethyl) amine, or a combination of several thereof.
Preferably, the beta-silyl styrene in the method for synthesizing chiral phenyl silanol is: beta-trimethylsilyl styrene or beta-triethylsilyl styrene or beta-p-methyltrimethylsilylstyrene or beta-p-chlorotrimethylsilyl styrene; the mol ratio of the beta-silyl styrene to the trichlorosilane is 1: 0.5 to 5; the mol ratio of the beta-silyl styrene to the metal palladium and chiral phosphine ligand is 1: 0.001-0.05: 0.001-0.1.
A method for synthesizing a 1, 2-chiral disilicon compound comprises the following steps: under the catalytic condition of a transition metal palladium compound, beta-silyl styrene and trichlorosilane generate asymmetric hydrosilation reaction, and then a 1, 2-chiral disilicon compound is obtained under the condition of a methyl magnesium chloride Grignard reagent; the reaction equation is as follows:
wherein R is hydrogen or methyl or chlorine, [ Si ] is trimethyl silicon or triethyl silicon;
the asymmetric hydrosilation reaction is as follows: stirring 176mg of beta-silyl styrene, trichlorosilane, a transition metal palladium compound and a chiral phosphine ligand at low temperature under the protection of nitrogen, reacting for 12-48 hours, and performing the next step after nuclear magnetism monitoring till the reaction is complete.
Preferably, the synthesis method of the 1, 2-chiral disilicon compound comprises the following steps:
s2.1, dissolving a product of the asymmetric hydrosilylation reaction in 5mL of tetrahydrofuran;
s2.2-10-50 ℃, adding 3.3mL of methyl magnesium chloride, and reacting at room temperature for 10-32 h;
s2.3 with saturated NH4Quenching reaction by using a Cl solution;
s2.4, extracting the reaction solution by using ethyl acetate, wherein the dosage of the reaction solution is 5 milliliters each time, and extracting for 3 times;
s2.5 combining the extracts in S2.4, and washing with saturated NaCl solution for 2 times, wherein 10 ml of saturated saline solution is used for each time;
s2.6 passing the organic phase over anhydrous Na2SO4Drying, concentrating, separating by glass column silica gel column chromatography, and purifying to obtain 1, 2-chiral disilicon compound.
Preferably, in the above method for synthesizing a 1, 2-chiral disilicon compound, the transition metal palladium compound is: [ PdCl (C)3H5)]2One or a combination of more of palladium acetate, palladium tetrakis (triphenylphosphine), palladium bis (triethylphosphine) dichloride and palladium bis (acetylacetone).
Preferably, in the above method for synthesizing a 1, 2-chiral disilicon compound, the chiral phosphine ligand is: (S) - (-) -2,2 '-bis [ bis (3, 5-di-tert-butylphenyl) phosphine ] -6,6' -dimethoxy-1, 1 '-biphenyl, (11BS) -N, N-bis (1-methylethyl) dinaphtho [2,1-D:1',2'-F ] [1,3,2] dioxaphosphin-4-amine, S- (-) -2,2' -bis (diphenylphosphino) -1,1 '-binaphthyl, (R) - (+) -2-diphenylphosphino-2' -methoxy-1, 1 '-binaphthyl, N-bis [ (R) -1-phenylethyl ] - [ (S) -1,1' -spiroindan-7, 7 '-diyl phosphoramidite, (R, S, S) - (3, 5-dioxa-4-phospha cyclohepta [2,1-a:3,4-a' ] dinaphthalen-4-yl) di (1-phenylethyl) amine, or a combination of several thereof.
Preferably, in the above method for synthesizing a 1, 2-chiral disilicon compound, the β -silyl styrene is: beta-trimethylsilyl styrene or beta-triethylsilyl styrene or beta-p-methyltrimethylsilylstyrene or beta-p-chlorotrimethylsilyl styrene; the mol ratio of the beta-silyl styrene to the trichlorosilane is 1: 0.5 to 5; the mol ratio of the beta-silyl styrene to the metal palladium and chiral phosphine ligand is 1: 0.001-0.05: 0.001-0.1.
The invention has the beneficial effects that: the research on the asymmetric hydrosilylation reaction conditions of transition metal catalyzed silicon-based phenyl olefin and trichlorosilane is disclosed, the preparation of a chiral double-silicon compound with high three-dimensional controllability is realized, and the chirality of a hydrosilylation product is characterized by converting trichlorosilane into hydroxyl through Fleming oxidation reaction. And then, a series of simple silicon-based conversion reactions are carried out to successfully prepare a plurality of stable 1, 2-chiral disilicon compounds, and the disilicon-containing chiral compounds can be used for preparing a series of chiral compounds through silicon-based conversion, so that the synthetic method has very important significance.
Detailed Description
The invention will be further illustrated with reference to specific embodiments:
example 1:
under the protection of inert gas, [ PdCl (C)3H5)]2(1mg,0.003mmol) and chiral phosphine ligand (3mg,0.006mol) were dissolved in beta-trimethylsilylstyrene (176mg,1mmol), stirred at room temperature for 30min until the solids were completely dissolved, and then at 0 deg.CTrichlorosilane (0.12mL,1.2mmol) was added and the reaction continued at this temperature for 24H with 1H NMR monitoring of the total conversion of the starting material to give a pale yellow solid (conversion)>99％)。
Then, the solid obtained above was dissolved in methanol/tetrahydrofuran (4mL:4mL), and KF (348.5mg,6mmol) and KHCO were added thereto at 0 deg.C3(600.7mg,6mmol)、30％H2O2(4mL), the system was heated to 50 ℃ and refluxed for 30min, saturated Na2S2O3The reaction was quenched with (5mL) solution, extracted with methyl tert-butyl ether (5mL x 3), combined organic phases washed with saturated NaCl (10 x 2), and organic phases washed with anhydrous Na2SO4Drying, concentrating and performing column chromatography to obtain a target compound 1:
target compound 1 was a white solid. mp is 41 ℃; rf 0.64(EtOAc/PE 1/5); 56% yield (in 2steps), 98% ee (Daicel AD-H0.46 x 25cm, n-Hexane i-PrOH 98:2,1mL/min,35 ℃,260nm,3.7MPa, tr (minor)9.2min, tr (major)10.1 min); [ α ] D22 (c 1.04, CH2Cl 2); 1H NMR (cdcl3,400mhz) δ 7.21-7.29 (m,5H),4.76(t, J ═ 8.0Hz,1H),2.01(brs,1H, OH),1.21(dd, J ═ 14.4,7.6Hz,1H),1.12(dd, J ═ 14.0,7.6Hz,1H), -1.03(s,9H).13C NMR (cdcl3,100mhz, plus, APT) δ (up)146.5,28.5.δ (down)128.6,127.7,126.0, 73.0, -1.01.ir (film)3365(OH),3084,3063,1671,1541,1492,775,700(Ph),862(CSi) cm "1;
example 2:
the preparation method is the same as example 1, the raw material is beta-triethyl silicon-based styrene, and a target compound 2 is obtained;
the objective compound 2 was a colorless oily liquid. Rf 0.55(EtOAc/PE 1/5); 45% yield (in 2steps), 97% ee (Daicel AD-H0.46 x 25cm, n-Hexane i-PrOH 98:2,1mL/min,35 ℃,260nm,3.9MPa, tr (minor)8.0min, tr (major)8.5 min); [ α ] D31 (c 1.19, CH2Cl 2); 1H NMR (cdcl3,400mhz) δ 7.24-7.36 (m,5H),4.82(t, J ═ 7.2Hz,1H),1.78(brs,1H, OH),1.24(dd, J ═ 12.0,8.0Hz,1H),1.16(dd, J ═ 12.0,8.0Hz,1H),0.87(t, J ═ 8.0Hz,9H), 0.35-0.51 (m,6H), 13C NMR (cdcl3,100mhz, plus, APT) δ (up)146.9,23.4,3.7 δ (down), 128.6,127.7,125.972.9,7.49.ir film) (3375 (OH),2952,2910,1541,1455,1415,772,700(Ph),833(CSi) cm-1;
example 3:
the preparation method is the same as example 1, the raw material is beta-p-methyl trimethylsilyl styrene, and a target compound 3 is obtained;
the objective compound 3 was a colorless oily liquid. Rf 0.51(EtOAc/PE 1/5); 53% yield (in 2steps), 93% ee (Daicel AD-H0.46 x 25cm, n-Hexane i-PrOH 98:2,1mL/min,35 ℃,270nm,4.1MPa, tr (minor)9.5min, tr (major)10.9 min); [ α ] D21 (c 1.02, CH2Cl 2); 1H NMR (Acetone,400MHz) δ 7.29(d, J ═ 7.8Hz,2H),7.15(d, J ═ 7.8Hz,2H), 4.81-4.86 (m,1H),3.98(d, J ═ 4.0Hz,1H),2.34(s,3H),1.24(dd, J ═ 14.3,8.4Hz,1H),1.13(dd, J ═ 14.3,8.4Hz,1H),0.00(s,9H), 13C NMR (Acetone,100MHz, plus, APT) δ (up)145.4,135.9,28.6 δ (down)128.6,125.7,71.4,20.3, -1.55.ir (ir) (33m) 49 (csoh), 3167,3145,1815,1748,1617,819,764(Ph), CSi (cm-1;
example 4:
the preparation method is the same as example 1, the raw material is beta-p-chlorotrimethylsilyl styrene, and a target compound 4 is obtained;
target compound 4 was a white solid. mp is 51 ℃; rf 0.55(EtOAc/PE 1/5); 48% yield (in 2steps), 96% ee (Daicel AD-H0.46 x 25cm, n-Hexane i-PrOH 98:2,1mL/min,35 ℃,260nm,3.7MPa, tr (minor)10.5min, tr (major)11.6 min); [ α ] D32 (c 1.63, CH2Cl 2); 1H NMR (cdcl3,400mhz) δ 7.28-7.33 (m,4H),4.82(t, J ═ 7.4Hz,1H),1.98(s,1H),1.24(dd, J ═ 14.1,7.5Hz,1H),1.14(dd, J ═ 14.3,7.5Hz,1H),0.03(s,9H), 13C NMR (cdcl3,100mhz, plus, APT) δ (up)145.0,133.1,28.5 δ (down)128.6,127.2,72.2, -1.0.ir (film)3258(OH),3258,3027,1792,1633,1577,764,702(Ph),725(CCl),832(CSi) cm "1;
example 5:
under the protection of inert gas, [ PdCl (C)3H5)]2(1.0mg,0.003mmol) and chiral phosphine ligand (3.0mg,0.006mol) were dissolved in beta-trimethylsilylstyrene (176.0mg,1mmol), stirred at room temperature for 30min until the solid was completely dissolved, then trichlorosilane (0.12mL,1.2mmol) was added at 0 deg.C, the reaction was continued for 24H at that temperature, 1H NMR monitored for complete conversion of the starting material to give a pale yellow solid (conversion rate)>99%). Then, the pale yellow solid obtained above was dissolved in tetrahydrofuran (5mL), MeMgCl (3.3mL) was added at 0 ℃ and reacted at room temperature for 24 hours with saturated NH4The reaction was quenched with Cl solution, extracted with ethyl acetate (5mL x 3), the combined organic phases washed with saturated NaCl (10 x 2), and the organic phases washed with anhydrous Na2SO4Drying, concentrating, and performing column chromatography to obtain target compound 5.
Target compound 5 was a white solid. mp is 45 ℃; rf ═ 0.84 (PE); 91% yield (in 2steps) [ α ] D-15(c1.00, CH2Cl 2); 1HNMR (cdcl3,400mhz) δ 7.20(t, J ═ 7.2Hz,2H), 7.01-7.07 (m,3H),2.07(dd, J ═ 15.1Hz,2.3,1H),1.07(t, J ═ 15.0Hz,1H),1.12(d, J ═ 15.2Hz,1H), -0.04(s,9H), -0.16(s,9H), 13C NMR (cdcl3,100mhz, plus, APT) δ (up)145.1,16.0 δ (down) 127.9,127.8,124.2,31.6, -1.0, -3.3.ir (fim) 3023,2953,1867,1790,1599,748,699(Ph),836(CSi) cm "1;
example 6:
the preparation method is the same as example 5, the raw material is beta-triethylsilyl styrene, and a target compound 6 is obtained;
the objective compound 6 was a colorless oily liquid. Rf ═ 0.83 (PE); 94% yield (in 2steps) [ α ] D-16(c 1.00, CH2Cl 2); 1H NMR (cdcl3,400mhz) δ 7.21(t, J ═ 7.4Hz,2H), 7.04-7.10 (m,3H),2.06(dd, J ═ 12.9,2.5Hz,1H), 0.89-1.09 (m,2H),0.82(t, J ═ 7.9Hz,9H), 0.26-0.39 (m,6H), -0.04(s,9H), -0.05(s,9H) 13C NMR (cdcl3,100mhz, plus, APT) δ (up)145.9,10.2,3.7.δ (down) 128.0,127.8,124.4,31.9,7.5, -3.2.ir film)2997,2952,1879,1796,1599,739,700(Ph),836(CSi) cm-1;
example 7:
the preparation method is the same as example 5, the raw material is beta-p-methyl trimethylsilyl styrene, and the target compound 7 is obtained;
the objective compound 7 was a colorless oily liquid. Rf ═ 0.79 (PE); 91% yield (in 2steps) [ α ] D-20(c 1.00, CH2Cl 2); 1H NMR (Acetone,400MHz) δ 7.21(d, J ═ 8.0Hz,2H),7.16(d, J ═ 8.1Hz,2H),2.43(s,3H),2.33(dd, J ═ 13.3,2.9Hz,1H),1.30(dd, J ═ 15.4,13.0Hz,1H),1.08(dd, J ═ 15.21,2.7Hz,1H),0.12(s,9H),0.00(s,9H), 13C NMR (Acetone,100MHz, plus, APT) δ (up)141.8,133.2,15.6 δ (down) 128.5,127.6,30.7,20.2, -1.5, -3.8. csfimm) 3019,2999,1734,1659,718,689(Ph), 7 (i) cm-1;
example 8:
the preparation method is the same as example 5, the raw material is beta-p-chlorotrimethylsilyl styrene, and a target compound 8 is obtained;
the objective compound 8 was a colorless oily liquid. Rf ═ 0.86 (PE); 91% yield (in 2steps) [ alpha ]]D-15(c 1.10,CH2Cl2)；1H NMR(Acetone,400MHz)δ7.26(d,J＝8.4Hz,2H),7.14(d,J＝8.4Hz,2H),2.24(dd,J＝13.1,2.3Hz,1H),1.15(dd,J＝15.2,13.1Hz,1H),0.94(dd,J＝15.2,2.3Hz,1H),-0.04(s,9H),-0.16(s,9H).13C NMR(Acetone,100MHz,plus,APT)δ(up)144.2,129.4,15.5.δ(down).129.3,127.8,30.8,-1.6,-4.0.IR(film)3016,2955,1762,1663,727,692(Ph),772(CCl),837(CSi)cm-1。
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. A method for synthesizing chiral phenyl silanol is characterized in that: under the catalytic condition of a transition metal palladium compound, carrying out asymmetric hydrosilation reaction on beta-silyl styrene and trichlorosilane, and then obtaining a chiral phenyl silanol compound under the condition of Fleming oxidation; the reaction equation is as follows:
wherein R is hydrogen or methyl or chlorine, [ Si ] is trimethyl silicon or triethyl silicon;
the asymmetric hydrosilation reaction is as follows: stirring 176mg of beta-silyl styrene, trichlorosilane, a transition metal palladium compound and a chiral phosphine ligand at low temperature under the protection of nitrogen, reacting for 12-48 hours, and performing the next step after nuclear magnetism monitoring till the reaction is complete.
2. The method for synthesizing chiral phenyl silanol as claimed in claim 1, wherein the method comprises the following steps: the synthesis method comprises the following steps:
s1.1, dissolving a product of asymmetric hydrosilylation in 4 mL/4 mL of methanol/tetrahydrofuran;
s1.2 KF (348.5mg,6mmol) and KHCO are added in sequence at-10-50 deg.C3(600.7mg,6mmol)、30％H2O24 mL；
S1.3, heating the system to 40-100 ℃, and carrying out reflux reaction for 20-100 min;
s1.4 with saturated Na2S2O3Quenching the reaction with 5mL of solution;
s1.5, extracting the reaction solution by using methyl tert-butyl ether, wherein the dosage of each reaction solution is 5 milliliters, and the extraction is carried out for 3 times;
s1.6 combining the extracts in S1.5, and washing with saturated NaCl solution for 2 times, 10 ml of saturated saline solution each time;
s1.7 passing the organic phase over anhydrous Na2SO4Drying, concentrating, separating by glass column silica gel column chromatography, and purifying to obtain chiral phenyl silanol compound.
3. The method for synthesizing chiral phenyl silanol as claimed in claim 1, wherein the method comprises the following steps: the transition metal palladium compound is: [ PdCl (C)3H5)]2One or a combination of more of palladium acetate, palladium tetrakis (triphenylphosphine), palladium bis (triethylphosphine) dichloride and palladium bis (acetylacetone).
4. The method for synthesizing chiral phenyl silanol as claimed in claim 1, wherein the method comprises the following steps: the chiral phosphine ligand is as follows: (S) - (-) -2,2 '-bis [ bis (3, 5-di-tert-butylphenyl) phosphine ] -6,6' -dimethoxy-1, 1 '-biphenyl, (11BS) -N, N-bis (1-methylethyl) dinaphtho [2,1-D:1',2'-F ] [1,3,2] dioxaphosphin-4-amine, S- (-) -2,2' -bis (diphenylphosphino) -1,1 '-binaphthyl, (R) - (+) -2-diphenylphosphino-2' -methoxy-1, 1 '-binaphthyl, N-bis [ (R) -1-phenylethyl ] - [ (S) -1,1' -spiroindan-7, 7 '-diyl phosphoramidite, (R, S, S) - (3, 5-dioxa-4-phospha cyclohepta [2,1-a:3,4-a' ] dinaphthalen-4-yl) di (1-phenylethyl) amine, or a combination of several thereof.
5. The method for synthesizing chiral phenyl silanol as claimed in claim 1, wherein the method comprises the following steps: the beta-silyl styrene is: beta-trimethylsilyl styrene or beta-triethylsilyl styrene or beta-p-methyltrimethylsilylstyrene or beta-p-chlorotrimethylsilyl styrene; the mol ratio of the beta-silicon-based styrene to the trichlorosilane is 1: 0.5 to 5; the mol ratio of the beta-silyl styrene to the metal palladium and chiral phosphine ligand is 1: 0.001-0.05: 0.001-0.1.
6. A method for synthesizing a 1, 2-chiral disilicon compound is characterized by comprising the following steps: under the catalytic condition of a transition metal palladium compound, beta-silyl styrene and trichlorosilane generate asymmetric hydrosilation reaction, and then a 1, 2-chiral disilicon compound is obtained under the condition of a methyl magnesium chloride Grignard reagent; the reaction equation is as follows:
wherein R is hydrogen or methyl or chlorine, [ Si ] is trimethyl silicon or triethyl silicon;
the asymmetric hydrosilation reaction is as follows: stirring 176mg of beta-silyl styrene, trichlorosilane, a transition metal palladium compound and a chiral phosphine ligand at low temperature under the protection of nitrogen, reacting for 12-48 hours, and performing the next step after nuclear magnetism monitoring till the reaction is complete.
7. A method of synthesizing a 1, 2-chiral disilicon compound according to claim 6, wherein: the synthesis method comprises the following steps:
s2.1, dissolving a product of the asymmetric hydrosilylation reaction in 5mL of tetrahydrofuran;
s2.2-10-50 ℃, adding 3.3mL of methyl magnesium chloride, and reacting at room temperature for 10-32 h;
s2.3 with saturated NH4Quenching reaction by using a Cl solution;
s2.4, extracting the reaction solution by using ethyl acetate, wherein the dosage of the reaction solution is 5 milliliters each time, and extracting for 3 times;
s2.5 combining the extracts in S2.4, and washing with saturated NaCl solution for 2 times, wherein 10 ml of saturated saline solution is used for each time;
s2.6 passing the organic phase over anhydrous Na2SO4Drying, concentrating, separating by glass column silica gel column chromatography, and purifying to obtain 1, 2-chiral disilicon compound.
8. The method of claim 6, wherein the chiral 1, 2-bis-silicon compound is prepared by the following steps: the transition metal palladium compound is: [ PdCl (C)3H5)]2One or a combination of more of palladium acetate, palladium tetrakis (triphenylphosphine), palladium bis (triethylphosphine) dichloride and palladium bis (acetylacetone).
9. The method of claim 6, wherein the chiral 1, 2-bis-silicon compound is prepared by the following steps: the chiral phosphine ligand is as follows: (S) - (-) -2,2 '-bis [ bis (3, 5-di-tert-butylphenyl) phosphine ] -6,6' -dimethoxy-1, 1 '-biphenyl, (11BS) -N, N-bis (1-methylethyl) dinaphtho [2,1-D:1',2'-F ] [1,3,2] dioxaphosphin-4-amine, S- (-) -2,2' -bis (diphenylphosphino) -1,1 '-binaphthyl, (R) - (+) -2-diphenylphosphino-2' -methoxy-1, 1 '-binaphthyl, N-bis [ (R) -1-phenylethyl ] - [ (S) -1,1' -spiroindan-7, 7 '-diyl phosphoramidite, (R, S, S) - (3, 5-dioxa-4-phospha cyclohepta [2,1-a:3,4-a' ] dinaphthalen-4-yl) di (1-phenylethyl) amine, or a combination of several thereof.
10. The method of claim 6, wherein the chiral 1, 2-bis-silicon compound is prepared by the following steps: the beta-silyl styrene is: beta-trimethylsilyl styrene or beta-triethylsilyl styrene or beta-p-methyltrimethylsilylstyrene or beta-p-chlorotrimethylsilyl styrene; the mol ratio of the beta-silicon-based styrene to the trichlorosilane is 1: 0.5 to 5; the mol ratio of the beta-silyl styrene to the metal palladium and chiral phosphine ligand is 1: 0.001-0.05: 0.001-0.1.
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