CN104478919B - A kind of method of synthesis of chiral silane compound - Google Patents

Abstract

The method discloses a method for synthesizing chiral silane compounds, using olefins and silicon hydrogen as raw materials, using chiral FeX ₂ ‑IPO complexes as catalysts, and reacting for 3 minutes in the presence of triethylsodium borohydride ‑48 The chiral silane compound is prepared in 1 hour, and the molar ratio of the alkene, silicon hydrogen, FeCl ₂ -IPO complex, and sodium triethylborohydride is 1:0.1-10:0.0005-0.05:0.0015-0.15; the reaction temperature is ‑30℃～80℃; the chiral silane compound obtained by the reaction can have great application value in many fields, such as derivatization to obtain chiral silanol and cyclosilane compound which are widely used in the field of materials, and in the field of biomedicine Widely existing chiral 2-hydroxyphenyl ethyl alcohol compounds or chiral benzofuran compounds.

Description

A kind of method of synthesizing chiral silane compound

technical field

The method relates to a method for synthesizing chiral silane compounds, in particular to a method for synthesizing optically active silane compounds.

Background technique

In recent years, transition metal-catalyzed reactions have been widely used in the fields of materials, chemicals, and medicines. However, due to the problem of metal residues, transition metal catalysts have many limitations, especially in the field of medicines. Iron-catalyzed reactions can avoid toxic heavy metals. Therefore, the development of efficient iron-catalyzed reactions is of great significance for the field of drug synthesis.

Silicon is the most important semiconductor material, and the hydrosilylation reaction is an important way to obtain organic silicon materials. The hydrosilation reaction has been widely used to prepare carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, carbon-nitrogen triple bonds, nitrogen-nitrogen double bonds and nitrogen-oxygen bonds. A series of organosilicon compounds [a) K.Tamao, N.Ishida, T.Tanaka, M.Kumada, Organometallics 1983,2,1694; b) I.Fleming, R.Henning, H.Plaut, J.Chem. Soc. Chem. Commun. 1984, 29.]. The hydrosilation reaction is also used as a protecting group and reducing agent in the synthesis of natural organic compounds [a) Y.Hatanaka, T.Hiyama, J.Org.Chem.1988, 53, 918; b) S.E.Denmark, C.S.Regens, Acc.Chem. Res. 2008, 41, 1486.].

However, how to efficiently prepare chiral silicon reagents has always been a hotspot and difficulty in the field of organic chemistry. In 1976, Kumada developed the asymmetric hydrosilylation reaction of alkenes [Yamamoto, K.; Hayashi, T.; Zembayashi, M.; Kumada, M. J. Organomet. Chem. 1976, 118, 161], but with low enantioselectivity (0.6-20.9% ee). Later, another research group tried and improved the asymmetric hydrosilylation reaction of olefins, but the effect was not very satisfactory, the substrate was very limited, and the enantioselectivity was also low. At the same time, catalysts such as precious metal rhodium were needed. [a] Tamao, K.; Tohma, T.; Inui, N.; Nakayama, O.; .; Bosnich, B.J.Am.Chem.Soc.1992,114,2121.c) Fu,P.-F.;Brard,L.;Li,Y.;Marks,T.J.J.Am.Chem.Soc.1995,117, 7157.].

Therefore, it is of great significance to develop high-efficiency and high-selectivity iron-catalyzed hydrosilylation of alkenes to synthesize chiral silane compounds, especially in the field of medicine and materials, which has broad application prospects.

Contents of the invention

The present invention is an improvement aimed at the deficiencies of the prior art, and provides an effective method for synthesizing silane compounds. The hydrosilation reaction of olefins and silicon hydrogen is catalyzed by chiral FeX ₂ -IPO complexes, and the substrate Wide range, suitable for aliphatic, aromatic olefins and large sterically hindered olefins, high efficiency (yield generally above 90%) enantioselective synthesis of optically active silanes (yield generally above 90%) compound method.

The present invention is achieved through the following technical solutions:

The invention discloses a method for synthesizing chiral silane compounds, using olefins and silicon hydrogen as raw materials, using chiral FeX ₂ -IPO complexes as catalysts, and reacting in the presence of triethylsodium borohydride for 3 minutes-48 A chiral silane compound is prepared in 1 hour, and the molar ratio of the olefin, silicon hydrogen, FeCl ₂ -IPO complex, and sodium triethylborohydride is 1:0.1-10:0.0005-0.05:0.0015-0.15; the reaction temperature is -30℃～80℃;

The structural formula of the olefin is R ¹ ≠ R ² ;

The structural formula of the pinacol borane is any one of Ph ₂ SiH ₂ or Ph ₃ SiH or PhSiH ₃ , Et ₂ SiH ₂ , (EtO) ₃ SiH, Et ₃ SiH;

Among them, R ¹ and R ² are optionally selected from C ₁ -C ₁₆ alkyl groups including cycloalkyl groups, substituted aryl groups Any one of them, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are optionally selected from H, halogen, C ₁ -C ₁₆ alkyl, C ₁ -C ₁₆ alkoxy, alkylthio Any one of them, X is any one of F, Cl, Br, I, OAc, CF ₃ SO ₃ , R ₃ is Ph ₂ H, PhH ₂ , Et ₃ , (EtO) ₃ , Et ₂ H Any one of the reaction products can be derivatized to obtain chiral silanol compounds, which can be widely used in the field of materials; chiral benzocyclosilane compounds can be widely used in the field of materials; chiral 2-hydroxybenzene Ethyl alcohol compounds can be widely used in the field of medicine; chiral benzofuran compounds can be widely used in the field of biomedicine.

As a further improvement, the FeX ₂ -IPO complex of the present invention is a chiral complex, and the product silane compound is optically active, and its structural formula is Where * represents a chiral carbon atom R ¹ , R ² is optionally selected from C ₁ -C ₁₆ alkyl groups including cycloalkyl groups, substituted aryl groups R ₃ is any one of Ph ₂ H, PhH ₂ , Et ₃ , (EtO) ₃ , and Et ₂ H.

As a further improvement, the structural formula of the FeX ₂ -IPO complex described in the present invention is an optically pure following compound or its enantiomer or racemate, R ⁸ is optionally selected from C ₁ -C ₁₆ hydrocarbon groups, naphthyl , substituted aryl, benzyl:

X is any one of F, Cl, Br, I, OAc, and CF ₃ SO ₃ .

As a further improvement, there is the participation of an organic solvent in the synthetic method of the present invention, and the organic solvent is benzene, carbon tetrachloride, toluene, tetrahydrofuran, ether, methylene chloride, acetonitrile, dioxane , petroleum ether, cyclohexane, n-hexane, ethyl acetate, chloroform, and N,N-diformamide.

As a further improvement, no solvent is added in the synthesis method described in the present invention.

As a further improvement, the molar ratio of the olefin, pinacol borane, FeX ₂ -IPO complex, and sodium triethylborohydride in the present invention is 1:0.5-2:0.005-0.05: 0.015-0.15, the reaction temperature is -10°C to 60°C, and the reaction time is 30 minutes to 12 hours.

As a further improvement, the molar ratio of olefin, silicon hydrogen, FeX ₂ -IPO complex, and sodium triethylborohydride in the present invention is 1:1:0.05:0.15, the reaction temperature is 25°C, and the reaction time is 1 hour.

As a further improvement, in the synthesis method described in the present invention, the reaction temperature is -30°C to 80°C.

As a further improvement, the obtained product is separated by recrystallization, thin layer chromatography, column chromatography or vacuum distillation.

As a further improvement, the synthesized chiral silane compound can be derivatized to obtain a chiral silanol compound, which can be widely used in the field of materials; chiral benzocyclosilane compounds can be widely used in the field of materials; The neutral 2-hydroxyphenyl ethyl alcohol compound can be widely used in the field of medicine; or the chiral benzofuran compound can be widely used in the field of biomedicine.

The beneficial effects of the present invention are as follows:

The method of the present invention provides an effective synthesis of optically active silanes from olefins and silicon hydrogen with high efficiency and high enantioselectivity using FeX ₂ -IPO complexes, especially chiral FeX ₂ -IPO complexes, as catalysts compound method. Compared with existing methods, this method is applicable to a variety of different types of olefins (aliphatic, aromatic and large steric hindered olefins), the reaction conditions are mild (it can occur at room temperature), and the reactivity is good (generally 1 hour. achievable), easy to operate, and high atom economy (100%). In addition, the catalyst used in the reaction is a complex of iron, without the addition of any other toxic transition metal (such as ruthenium, rhodium, palladium, etc.) salts, and the yield of the reaction is also good, generally 80% to 98%. , enantioselectivity is also high, generally 80% to 99%. Moreover, the chiral silane compounds obtained from the reaction can have great application value in many fields, such as chiral silanols and cyclosilane compounds that can be widely used in the field of materials through derivatization, and chiral silane compounds that are widely used in the field of biomedicine. 2-hydroxyphenyl ethyl alcohol compounds or chiral benzofuran compounds.

Detailed ways

The method of the present invention is an effective method for synthesizing silane compounds from olefins and silicon hydrogen. The method uses FeX ₂ -IPO complex as catalyst. Especially when the chiral FeX ₂ -IPO complex is used as a catalyst, optically active silane compounds can be synthesized from olefins and silicon hydrogen with high efficiency and high enantioselectivity.

The general molecular formula of the synthetic silane compound of the inventive method is: When a chiral FeX ₂ -IPO complex is used as a catalyst, the synthesized silane compound is optically active, and its general formula is where * represents a chiral carbon atom. R ¹ , R ² are optionally selected from C ₁ -C ₁₆ hydrocarbon groups including cycloalkyl groups, naphthyl groups, substituted aryl groups Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are optionally selected from H, halogen, C ₁ -C ₁₆ alkyl, C ₁ -C ₁₆ alkoxy, amino or substituted aryl, R ₃ Any one of Ph ₂ H, PhH ₂ , Et ₃ , (EtO) ₃ , and Et ₂ H. The above-mentioned halogen includes F, Cl, Br or I, and the above-mentioned hydrocarbon group can be an alkyl group, a cycloalkyl group, or a benzyl group.

The silane compound of the present invention is based on olefin and silicon hydrogen as raw materials, in the presence of sodium triethylborohydride, in an organic solvent or without a solvent, with FeX ₂ -IPO complex, especially FeX ₂ -IPO complex Prepared as a catalyst reaction, it can be represented by the following formula:

The structural formula of alkenes is: Wherein, R ¹ and R ² are as described above; the structural formula of silicon hydrogen is any one of Ph ₂ SiH ₂ or Ph ₃ SiH or PhSiH ₃ , Et ₂ SiH ₂ , (EtO) ₃ SiH, Et ₃ SiH; the catalyst The general structural formula of is (for any optically pure structure, or its enantiomer or racemate, not limited by the illustration)

R ⁸ is optionally selected from C ₁ -C ₁₆ hydrocarbyl, naphthyl, substituted aryl, benzyl.

The molar ratio of olefin, silicon hydrogen, FeX ₂ -IPO complex, and sodium triethylborohydride is 1:0.1-10:0.0005-0.05:0.0015-0.3, further 1:0.5-2:0.005-0.05 : 0.015-0.15; especially recommended molar ratio of reaction: olefin, silicon hydrogen, FeX ₂ -IPO complex, triethyl sodium borohydride molar ratio of 1:1:0.05:0.15. The reaction temperature is recommended to be -30°C to 80°C, further recommended to be -10°C to 60°C, and 25°C is especially recommended. The reaction time is recommended to be 3 minutes to 48 hours, further recommended to be 30 minutes to 12 hours, and especially recommended to be 1 hour. Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above.

The alkyl group mentioned in the present invention is recommended to have a carbon number of 1-16, further recommended to have a carbon number of 1-10, especially recommended to be a group with a carbon number of 1-6. The cycloalkyl groups mentioned in the present invention all recommend groups with 3-16 carbons, further recommend 3-10 carbons, especially recommend 3-6 carbons. The aryl mentioned in the present invention refers to phenyl, naphthyl and heteroaryl containing N, O, S.

The reaction of the inventive method can be carried out under solventless, also can carry out in polar or nonpolar solvent, as benzene, carbon tetrachloride, toluene, tetrahydrofuran, ether, methylene dichloride, acetonitrile, dioxane , petroleum ether, cyclohexane, n-hexane, ethyl acetate, chloroform, N,N-diformamide, etc.

The method of the present invention can be separated by recrystallization, thin layer chromatography, column chromatography or vacuum distillation. The inventive method provides some new silane compounds synthetic method.

The technical scheme of the present invention is further specifically described below by specific examples:

Example 1: Hydrosilylation of alkenes and silicon hydrogen catalyzed by chiral FeX ₂ -IPO complexes

Add (chiral) FeX ₂ -IPO complex (0.01 mmol), alkene (1 mmol), silicon hydrogen (1 mmol), diethyl ether (1 mL), triethyl borohydrogenate to a dry reaction tube at -30°C Sodium (0.03mmol), then stirred at room temperature for 1 hour and separated by column chromatography to obtain the product.

P1: (S)-(-)-diphenyl(2-phenylpropyl)silane

(or its enantiomers)

Oily liquid, 98% yield, [α] ²⁰ _D =-22.8 (c 1.0, CHCl ₃ ), 90.9% ee; ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.60-7.46 (m, 4H), 7.42-7.29(m,6H),7.28-7.20(m,2H),7.20-7.10(m,3H),4.77(t,J＝3.6 Hz,1H),3.02-2.88(m,1H),1.65- 1.48(m, 2H), 1.31(d, 3H); ¹³ CNMR(100.6 MHz, CDCl ₃ ): δ149.0, 135.1(d, J=5.8 Hz), 134.5(d, J=19.0 Hz), 129.5(d, J=3.1 Hz), 128.3, 127.9, 126.6, 125.9, 36.2, 25.2, 22.6; HRMS (EI) calculated for [C ₂₁ H ₂₂ Si] ⁺ requires m/z 302.1491, found m/z 302.1487.

P2: (S)-(-)-diphenyl(2-phenylbutyl)silane

Oily liquid, 96% yield, [α] ²⁰ _D = -24.4 (c 0.99, CHCl ₃ ), 93.7% ee, determined by HPLC, HPLC conditions: Chiralcel OJ-H, n-hexane/i-PrOH = 98/2 , 0.5 mL/min, n=220nm, t _r 10.3(major), 14.6(minor); ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.55-7.47(m,2H), 7.47-7.41(m, 2H),7.40-7.26(m,6H),7.25-7.19(m,2H),7.18-7.05(m,3H),4.65(t,J＝3.6 Hz,1H),2.70-2.57(m,1H) ,1.84-1.69(m,1H),1.69-1.66(m,2H),1.55-1.42(m,1H),0.71(t,J=7.2 Hz,3H); ¹³ C NMR(100.6 MHz,CDCl ₃ ) : δ146.6, 135.1 (d, J = 16.6 Hz), 134.6 (d, J = 4.6 Hz), 129.4 (d, J = 10.5 Hz), 128.2, 127.9 (d, J = 7.4 Hz), 127.5, 125.9, 43.6 , 32.4, 20.7, 12.1; ²⁹ Si NMR (79 MHz, CDCl ₃ ): δ-15.5; HRMS (EI) calculated for [C ₂₂ H ₂₄ Si] ⁺ requires m/z 316.1647, found m/z 316.1652.

P3: (S)-(-)-diphenyl(2-(p-tolyl)propyl)silane

Oily liquid, 87% yield, [α] ²⁰ _D =-28.7 (c 1.02, CHCl ₃ ), 93.6% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.60-7.45 (m, 4H), 7.42-7.27(m,6H),7.05(s,4H),4.77(t,J＝3.6 Hz,1H),3.00-2.85(m,1H),2.30(s,3H),1.62-1.44(m, 2H), 1.29(d, J=6.8 Hz, 3H); ¹³ CNMR(100.6MHz, CDCl ₃ ): δ146.0, 135.3, 135.1(d, J=5.5 Hz), 134.6(d, J=20.1Hz), 129.4 (d, J=5.0Hz), 129.0, 127.9 (d, J=1.6 Hz), 126.4, 35.8, 25.3, 22.7, 21.0; HRMS(EI) calculated for[C ₂₂ H ₂₄ Si] ⁺ requires m/z 316.1647 ,found m/z 316.1650.

P4: (S)-(-)-diphenyl(2-(m-tolyl)propyl)silane.

Oily liquid, 92% yield, [α] ²⁰ _D =-18.9 (c 1.04, CHCl ₃ ), 91.6% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.57-7.46 (m, 4H), 7.42-7.27(m,6H),7.18-7.08(m,1H),7.02-6.92(m,3H),4.78(t,J＝4.0 Hz,1H),2.98-2.85(m,1H),2.29( s, 3H), 1.61-1.47 (m, 2H), 1.30 (d, J = 6.8Hz, 3H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ148.9, 137.8, 135.1 (d, J = 5.2Hz) ,134.6(d,J=22.3Hz),129.4(d,J=3.2 Hz),128.2,127.9,127.4,126.6,123.6,36.1,25.1,22.6,21.4; HRMS(EI) calculated for[C22H24Si]+requires m/z 316.1647, found m/z 316.1650.

P5: (S)-(-)-diphenyl(2-(o-tolyl)propyl)silane.

Oily liquid, 96% yield, [α] ²⁰ _D =-0.2 (c 1.0, CHCl ₃ ), 98.3% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.56-7.47 (m, 4H), 7.41-7.26(m,7H),7.20-7.11(m,1H),7.09-7.02(m,2H),4.80(t,J=4.0 Hz,1H),3.25-3.11(m,1H),2.08( s, 3H), 1.62-1.45 (m, 2H), 1.27 (d, J = 6.8 Hz, 3H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ147.1, 135.0 (d, J = 3.8 Hz), 134.6 (d, J=6.2 Hz), 134.4, 130.1, 129.5, 127.9, 126.2, 125.5, 125.3, 30.8, 24.3, 21.8, 19.2; HRMS(EI) calculated for [C ₂₂ H ₂₄ Si] ⁺ requires m/z 316.1647 ,found m/z316.1648.

P6: (S)-(-)-(4-(1-(diphenylsilyl)propan-2-yl)phenoxy)triisopropylsilane

Oily liquid, 88% yield, [α] ²⁰ _D =-8.6 (c 1.02, CHCl ₃ ), 93.8% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.57-7.44 (m, 4H), 7.41-7.28(m,6H),6.98(d,J＝8.2Hz,2H),6.75(d,J＝8.4Hz,2H),4.73(t,J＝3.8Hz,1H),2.95-2.81(m ,1H),1.59-1.44(m,2H),1.34-1.18(m,6H),1.09(d,J＝7.2 Hz,18H); ¹³ C NMR(100.6 MHz,CDCl ₃ ):δ154.0,141.3,135.1 (d, J=9.1Hz), 134.7(d, J=8.1 Hz), 129.4(d, J=2.0 Hz), 127.9, 127.3, 119.5, 35.4, 25.5, 22.8, 17.9, 12.7; HRMS(EI) calculated for[C ₃₀ H ₄₂ OSi ₂ ] ⁺ requires m/z474.2744, found m/z47432745.

P7: (S)-(-)-(2-(4-fluorophenyl)propyl)diphenylsilane

Oily liquid, 95% yield, [α] ²⁰ _D =-18.2 (c 0.96, CHCl ₃ ), 88.6% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.59-7.44 (m, 4H), 7.42-7.26(m,6H),7.14-7.04(m,2H),6.97-6.85(m,2H),4.75(t,J=3.8 Hz,1H),3.00-2.87(m,1H),1.59- 1.44(m,2H),1.29(d,J=6.8Hz,3H); ¹³ CNMR(100.6 MHz,CDCl ₃ ):δ161.2(d,J=243.7 Hz),144.4(d,J=2.6Hz) ,135.0(d,J=7.4Hz),134.3(d,J=15.2Hz),129.5(d,J=5.4Hz),128.0(d,J=1.6Hz),127.9(d,J=4.2Hz) , 114.9 (d, J=21.0 Hz), 35.6, 25.5, 22.7; ¹⁹ F NMR (CDCl ₃ , 376 MHz): δ-117.5; HRMS (EI) calculated for [C ₂₁ H ₂₁ FSi] ⁺ requires m/z320 .1397, found m/z 320.1396.

P8: (S)-(+)-(2-(2-methoxyphenyl)propyl)diphenylsilane.

Oily liquid, 97% yield, [α] ²⁰ _D =+7.1 (0.99, CHCl ₃ ), 93.6% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.59-7.45 (m, 4H), 7.41 -7.26(m,6H),7.24-7.17(m,1H),7.16-7.07(m,1H),6.94-6.84(m,1H),6.75(d,J＝8.0 Hz,1H),4.79(t ,J=3.8 Hz,1H),3.68(s,3H),3.51-3.38(m,1H),1.67-1.55(m,1H),1.53-1.40(m,1H),1.29(d,J=6.8 Hz, 3H); ¹³ CNMR (100.6 MHz, CDCl ₃ ): δ156.5, 137.0, 135.1 (d, J=8.4 Hz), 134.8, 129.3, 127.8, 126.6, 126.5, 120.5, 110.3, 55.0, 28.7, 23.2, 21.4 ; HRMS(EI) calculated for [C ₂₂ H ₂₄ OSi] ⁺ requires m/z 332.1596, found m/z 332.1600.

P9: (S)-(+)-(2-(2-bromophenyl)propyl)diphenylsilane.

Oily liquid, 94% yield, [α] ²⁰ _D =+0.8 (0.99, CHCl ₃ ), 95.0% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.58-7.47 (m, 6H), 7.46 -7.40(m,1H),7.40-7.28(m,6H),7.24-7.17(m,1H),4.88(t,J=3.6 Hz,1H),3.52-3.40(m,1H),1.65-1.50 (m, 2H), 1.29 (d, J=6.4Hz, 3H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ148.6, 135.0 (d, J=3.7 Hz), 134.2 (d, J=61.8 Hz) , 132.0, 129.6, 128.0 (d, J=3.7 Hz), 127.5, 125.7, 125.42, 125.36, 31.0, 24.9, 22.7; HRMS (EI) calculated for [C ₂₁ H ₂₁ BrSi] ⁺ requires m/z 380.0596, found m/z380.0599.

P10: (S)-(-)-(2-(naphthalen-2-yl)propyl)diphenylsilane.

Oily liquid, 88% yield, [α] ²⁰ _D =-41.0 (c 1.05, CHCl ₃ ), 90.1% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.81-7.69 (m, 3H), 7.57-7.47(m,5H),7.46-7.26(m,9H),4.78(t,J＝4.0Hz,1H),3.19-3.06(m,1H),1.72-1.56(m,2H),1.39( d, J = 6.8 Hz, 3H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ146.3, 135.1 (d, J = 8.3 Hz), 134.5 (d, J = 19.9 Hz), 133.6, 132.2, 129.5 (d , J=6.0 Hz), 128.0, 127.9, 127.6, 127.5, 125.8, 125.5, 125.1, 124.6, 36.3, 25.1, 22.4; HRMS (EI) calculated for [C ₂₅ H ₂₄ Si] ⁺ requires m/z 352.1647, found m/z 352.1649.

P11: (S)-(+)-(2-(naphthalen-1-yl)propyl)diphenylsilane.

Oily liquid, 99% yield, [α] ²⁰ _D =+56.8 (c 1.0, CHCl ₃ ), >99% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.90-7.78 (m, 2H) ,7.66(d,J=7.8 Hz,1H),7.62-7.53(m,2H),7.53-7.26(m,12H),4.92(t,J=3.8 Hz,1H),3.87-3.74(m,1H ),1.81-1.71(m,1H),1.63-1.56(m,1H),1.46(d,J＝6.8 Hz,3H); ¹³ C NMR(100.6 MHz,CDCl ₃ ):δ145.2,135.1(d,J =9.8 Hz), 134.4(d, J=13.7 Hz), 133.9, 131.0, 129.6(d, J=10.4 Hz), 128.9, 128.0, 127.9, 126.4, 125.6, 125.2, 123.1, 122.3, 30.1, 23.9, 22.3 ; HRMS(EI) calculated for [C ₂₅ H ₂₄ Si] ⁺ requires m/z 352.1647, found m/z 352.1651.

P12: (S)-(-)-(2-cyclohexyl-2-phenylethyl)diphenylsilane.

Oily liquid, 96% yield, [α] ²⁰ _D =-31.8 (c 0.98, CHCl ₃ ), 96.1% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.52-7.43 (m, 2H), 7.42-7.22(m,8H),7.22-7.09(m,3H),7.04-6.97(m,2H),4.50-4.40(m,1H),2.55-2.41(m,1H),1.99-1.86(m ,1H),1.82-1.66(m,2H),1.65-1.52(m,2H),1.50-1.36(m,3H),1.24-1.12(m,1H),1.10-0.96(m,2H),0.94 -0.79 (m, 1H), 0.79-0.64 (m, 1H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ144.9, 135.0 (d, J＝29.9 Hz), 134.8 (d, J＝47.8Hz), 129.3 (d, J = 17.2 Hz), 128.6, 127.9, 127.8 (d, J = 4.2 Hz), 125.9, 47.9, 45.3, 31.3, 30.5, 26.6, 26.48, 26.46, 16.7; HRMS (EI) calculated for [C ₂₆ H ₃₀ Si] ⁺ requires m/z370.2117, found m/z 370.2121.

P13: (R)-(-)-tert-butyl((5-(diphenylsilyl)-4-phenylpentyl)oxy)dimethylsilane.

Oily liquid, 93% yield, [α] ²⁰ _D =-14.8 (c 1.03, CHCl ₃ ), 97.0% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.54-7.46 (m, 2H), 7.46-7.41(m,2H),7.41-7.25(m,6H),7.25-7.18(m,2H),7.17-7.11(m,1H),7.11-7.04(m,2H),4.65(t,J ＝3.6 Hz, 1H), 3.46(t, J＝6.6 Hz, 2H), 2.77-2.65(m, 1H), 1.86-1.73(m, 1H), 1.71-1.45(m, 3H), 1.41-1.20( m, 2H), 0.85(s, 9H), -0.03(d, J=1.6 Hz, 6H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ146.6, 135.1(d, J=16.1 Hz), 134.5( d,J=4.8 Hz),129.4(d,J=11.1 Hz),128.2,127.9(d,J=7.7Hz),127.5,126.0,63.0,41.7,35.7,30.8,26.0,21.3,18.3,-5.3 ; HRMS (EI) calculated for [C ₂₉ H ₄₀ OSi ₂ ] ⁺ requires m/z 460.2618, found m/z 460.2618.

P14: (S)-(-)-(3-(4-methoxyphenyl)-2-methylpropyl)diphenylsilane.

Oily liquid, 92% yield, [α] ²⁰ _D =-11.8 (c 1.0, CHCl ₃ ), 44.8% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.56-7.45 (m, 4H), 7.41-7.29(m,6H),6.97(d,J=8.4Hz,2H),6.79(d,J=8.4Hz,2H),4.94(m,1H),3.77(s,3H),2.62-2.63 (m,1H),2.48-2.39(m,1H),2.00-1.86(m,1H),1.35-1.24(m,1H),1.07-0.98(m,1H),0.93(d,J＝6.6 Hz ,3H); ¹³ CNMR(100.6 MHz, CDCl ₃ ): δ157.7, 135.1(d, J=8.0 Hz), 134.8(d, J=43.9 Hz), 133.3, 130.1, 129.4(d, J=1.6 Hz), 127.9, 113.5, 55.2, 45.6, 32.0, 22.3, 19.9; HRMS (EI) calculated for [C ₂₃ H ₂₆ OSi] ⁺ requires m/z 346.1753, found m/z 346.1750.

Embodiment 2: product oxidation synthesis silanol compound (application example)

A 20 mL reaction tube was charged with silicon hydride (1 mmol), trifluoroacetophenone (0.1 mmol), tBuOH (0.5 mL), saturated NaHCO ₃ solution (0.5 mL), CH ₃ CN (0.08 mL), 30% H ₂ O ₂ in water (0.11 mL), and the silanol product was isolated after stirring at room temperature for 12 hours. (S)-(-)-(3-methyl-2-phenylbutyl)diphenylsilanol: colorless oily liquid, 94% yield, Optical Rotation: [α] ²⁰ _D =-23.8 (c 0.99, CHCl ₃ ), 98.1% ee, ¹ H NMR (400.1MHz, CDCl ₃ ): δ7.60-7.49(m,2H),7.49-7.43(m,2H),7.43-7.14(m,9H),7.08-6.99(m,2H) ,2.55-2.43(m,1H),1.86-1.74(m,1H),1.69(dd,J=15.0,3.6 Hz,1H),1.55-1.43(m,1H),1.21(s,1H),0.95 (d, J=6.4 Hz, 3H), 0.67 (d, J=6.4 Hz, 3H); ¹³ C NMR (100.6MHz, CDCl ₃ ): δ145.4, 136.5 (d, J=67.6 Hz), 133.9(d, J=22.5 Hz), 129.6, 128.3 (d, J=9.5 Hz), 127.8, 127.7, 126.4, 48.2, 35.8, 20.7, 20.4, 19.8; HRMS(EI) calculated for[C ₂₃ H ₂₆ OSi] ⁺ requiresm/ z 346.1753, found m/z 346.1752.

Embodiment 3: Product derivatization synthesis benzocyclosilane compound (application example)

Silane compound (0.5mmol), [Ir(OMe)(cod)] ₂ (0.01mmol), 4,4-di-tert-butylbipyridine (0.02mmol), 2-norbornene (0.6 mmol), THF (2.5 mL), the product dihydrobenzosiloles was isolated after reacting at 80° C. for 12 hours. (S)-(-)-3-methyl-1,1-diphenyl-2,3-dihydro-1H-benzo[b]silole: 89% yield, [α] ²⁰ _D =-8.6 (c 1.04, CHCl ₃ ), 91.5%ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.66 (d, J=7.2 Hz, 1H), 7.64-7.58 (m, 2H), 7.58-7.49 (m, 2H), 7.45-7.29(m,8H),7.26-7.21(m,1H),3.51-3.37(m,1H),1.79(dd,J=15.2,8.0 Hz,1H),1.38(d,J=6.8 Hz, 3H), 1.17(dd, J＝15.0, 6.0 Hz, 1H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ158.9, 136.1, 135.5(d, J＝33.6 Hz), 135.1(d, J＝7.8 Hz ), 133.2, 130.1, 129.5 (d, J＝1.8 Hz), 127.9, 126.1, 124.9, 38.4, 25.0, 20.6; HRMS (EI) calculated for [C ₂₁ H ₂₀ Si] ⁺ requires m/z 300.1334, found m /z 300.1337.

Embodiment 4: Product derivatization synthesis 2-hydroxyphenyl ethyl alcohol compound (application example)

Under ice-cooling, potassium tert-butoxide (1.8mmol), THF (2mL), tert-butanol peroxide (1.8mmol) were added into a 10mL reaction tube, and after stirring for ten minutes, a benzocyclosilane compound (0.3 mmol), TBAF (1.8mmol), 2-hydroxyphenyl ethyl alcohol products were isolated after 12 hours of reaction at 70°C. (S)-(+)-2-(1-hydroxypropan-2-yl)phenol: oily liquid, 86% yield, [α] ²⁰ _D = +7.4 (c 1.5, CHCl ₃ ), 91.5% ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.15-7.05 (m, 2H), 6.94-6.79 (m, 2H), 5.25 (br, 2H), 3.85 (dd, J = 10.0, 4.0 Hz, 1H), 3.72-3.62 (m, 1H), 3.30-3.15 (m, 1H), 1.28 (d, J=7.2 Hz, 3H); ¹³ C NMR (100.6 MHz, CDCl ₃ ): δ154.6, 130.6, 127.8, 127.7, 120.6 , 116.8, 69.0, 36.7, 15.7; HRMS(EI) calculated for [C ₂₁ H ₂₀ Si] ⁺ requires m/z 152.0837, found m/z 152.0838.

Embodiment 5: Product derivatization synthesis benzofuran compound (application example)

Add 2-hydroxyphenylethyl alcohol compound (0.4mmol), THF (2mL), triphenylphosphine (0.48mmol), and diisopropyl azodicarboxylate (0.6mmol) into the 10mL reaction tube and stir at room temperature for 2 The benzofuran product was isolated after hours. (S)-(+)-3-methyl-2,3-dihydrobenzofuran: 83% yield, [α] ²⁰ _D ＝+10.4(c 1.1, CHCl ₃ ), 91.5%ee, ¹ H NMR (400.1 MHz, CDCl ₃ ): δ7.12(d, J=7.2 Hz, 2H), 6.94-6.85(m, 2H), 3.99-3.89(m, 1H), 3.75-3.69(m, 1H), 3.26-3.21(m ,1H), 1.31 (d, J=7.2 Hz, 3H); ¹³ C NMR (100.6MHz, CDCl ₃ ): δ159.6, 128.1, 127.1, 125.1, 120.3, 109.4, 79.6, 37.2, 21.9; HRMS (EI) calculated for[C ₂₁ H ₂₀ Si] ⁺ requires m/z 134.0732, found m/z 134.0730.

Finally, it should also be noted that what is listed above are only specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many variations are possible. All deformations that can be directly derived or associated by those skilled in the art from the content disclosed in the present invention should be considered as the protection scope of the present invention.

Claims (7)

1. A method for synthesizing chiral silane compounds, characterized in that alkene and silicon hydrogen are raw materials, with chiral FeX ₂ -IPO complexes are catalysts, and in the presence of sodium triethylborohydride, react for 3 minutes- The chiral silane compound was prepared in 48 hours, the molar ratio of the alkene, silicon hydrogen, FeCl ₂ -IPO complex, and sodium triethylborohydride was 1:0.1-10:0.0005-0.05:0.0015-0.15, and the reaction temperature -30℃～80℃; The structural formula of the olefin is R ¹ ≠ R ² ; The structural formula of silicon hydrogen is any one of Ph ₂ SiH ₂ or Ph ₃ SiH or PhSiH ₃ , Et ₂ SiH ₂ , (EtO) ₃ SiH, Et ₃ SiH; Wherein, R ¹ and R ² are optionally selected from C ₁ -C ₁₆ alkyl groups including cycloalkyl groups, Any one of them, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are optionally selected from H, halogen, C ₁ -C ₁₆ alkyl, C ₁ -C ₁₆ alkoxy, alkylthio Any one of them, X is any one of F, Cl, Br, I, OAc, CF ₃ SO ₃ , the reaction product can be derivatized to obtain chiral silanol compounds, chiral benzocyclosilanes Compounds, chiral 2-hydroxyphenyl ethyl alcohol compounds, chiral benzofuran compounds, the structural formula of the FeX ₂ -IPO complex is optically pure following compound or its enantiomer or elimination Spin body, R ⁸ is optionally selected from C ₁ -C ₁₆ hydrocarbyl, naphthyl, benzyl: X is any one of F, Cl, Br, I, OAc, and CF ₃ SO ₃ . 2. The method for synthesizing chiral silane compounds according to claim 1, characterized in that, the FeX ₂ -IPO complex is a chiral complex, and the product silane compounds are optically active, Its structural formula is Wherein * represents chiral carbon atom R ¹ , R ² is as described in claim 1, R ₃ is any one of Ph ₂ H, PhH ₂ , Et ₃ , (EtO) ₃ , Et ₂ H. 3. the method for synthetic chiral silane compound according to claim 1, is characterized in that, there is the participation of organic solvent in described synthetic method, and described organic solvent is benzene, carbon tetrachloride, toluene, tetrahydrofuran (THF), diethyl ether , any one of dichloromethane, acetonitrile, dioxane, petroleum ether, cyclohexane, n-hexane, ethyl acetate, chloroform, and N,N-diformamide. 4. the method for synthetic chiral silane compound according to claim 1, is characterized in that, does not add any solvent in the described synthetic method. 5. according to the method for the described synthetic chiral silane compound of claim 1 or 2 or 3 or 4, it is characterized in that, described alkene, silicon hydrogen, FeX ₂ -IPO complexes, sodium triethylborohydride The molar ratio is 1:0.5-2:0.005-0.05:0.015-0.15, the reaction temperature is -10°C-60°C, and the reaction time is 30 minutes-12 hours. 6. The method for synthesizing chiral silane compounds according to claim 5, characterized in that the molar ratio of the alkene, silicon hydrogen, FeX ₂ -IPO complex, and sodium triethylborohydride is 1:1 :0.05:0.15, the reaction temperature is 25°C, and the reaction time is 1 hour. 7. The method for synthesizing chiral silane compounds according to claim 5, wherein the obtained product is separated through recrystallization, thin-layer chromatography, column chromatography or vacuum distillation.