Chiral hydrosilane compound as well as preparation method and application thereof

Abstract

The invention discloses a chiral hydrosilane compound as well as a preparation method and application thereof. The structural formula of the chiral hydrosilane compound is shown as a formula (I). The chiral hydrosilane compound can be prepared by two methods, one method comprises the following steps: synthesizing tert-butyldihydrosilane from cheap and easily available phenyl silane through a Grignard reagent reaction, adding a ligand and hexamethyldisilylamino potassium to react with benzyl alcohol in a copper tetracyano hexafluorophosphonate catalysis manner, and carrying out reduced pressure distillation to obtain the chiral hydrosilane compound. And finally, synthesizing a hydrogen silane compound with chirality. And the other method comprises the step of adding a brominated compound and cesium carbonate in a copper metal catalysis process to generate the chiral hydrosilane compound. According to the invention, the range of the product is widened to a great extent, and a foundation is laid for subsequent application and transformation. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of organic synthesis, and specifically relates to a chiral hydrosilane compound, a preparation method thereof, and an application thereof. Background Art

[0002] In the past decade or so, organosilicon compounds have been important components in agrochemicals, odorants, pharmaceuticals, advanced materials, and industrial chemicals. Siloxanes and alkoxysilanes (such as silyl ethers) are one of the important skeletons of organosilicon compounds, and are widely used as special monomers in silicon-based materials, as well as valuable protecting groups, reagents, and intermediates in organic synthesis. At present, scientific researchers have provided a new strategy for the palladium-catalyzed synthesis of chiral hydrosilane compounds to introduce more complex structures and richer stereoselectivity.

[0003] With the vigorous development of transition metal catalytic systems, the reaction system for metal-catalyzed construction of silicon-oxygen bonds has become increasingly perfect. How to further introduce more heteroatoms into the original structure of chiral hydrosilane compounds and convert them into heterocyclic compounds containing multiple heteroatoms such as silicon, oxygen, and nitrogen through different reaction conditions is a path worthy of in-depth exploration. Such heterocycles play important roles as key structural units or basic skeletons in synthetic chemistry, biochemistry, and medicinal chemistry, and can also play important roles in the production of various bioactive molecules, drugs, and natural products. Summary of the Invention

[0004] The first object of the present invention is to provide a chiral hydrosilane compound in view of the deficiencies of the prior art.

[0005] The present invention is achieved by the following technical solutions:

[0006] A chiral hydrosilane compound, characterized in that the structure is shown in formula (I):

[0007]

[0008] In the formula, * represents a chiral silicon atom;

[0009] R1 is one of tert-butyl and o-methoxyphenyl;

[0010] R2 is one of C 6-14 aryl, C4 heterocycle, C 13 diphenylmethane.

[0011] Further, the structural formula of the compound is selected from one of the following formulas (Ia) to (Ir):

[0012]

[0013] The second object of the present invention is to provide a preparation method of the above-mentioned chiral hydrosilane compound. Compared with the existing synthesis methods, the raw materials required by the present invention are low in cost and easy to obtain, the synthesis process is simple, it has a good yield, and a very wide range of substrates, and more complex and rich drug molecules and functional molecular fragments can be introduced, laying a foundation for the diversity of subsequent asymmetric transformations.

[0014] The preparation method includes Method A and Method B; specifically, Method A includes the following steps:

[0015] Step (1): Dissolve compound S1 in water to obtain an S1 solution, dissolve compound S2 in absolute ethanol, and then drop it into the S1 solution (absolute ethanol: water = 60:40 mL). Then heat it to 70 °C, carry out reflux stirring for 12 h, add water, place it at 0 °C for 5 h, filter the precipitated white solid to obtain the product, that is, compound S3;

[0016] Step (2): Under a nitrogen atmosphere, dissolve compound S3 in a mixed solution of toluene and acetonitrile (volume ratio 15:150) at 0 °C, then add zinc powder and trifluoroacetic acid, and stir at room temperature for about 24 h. Add triethylamine for acid-base neutralization, filter to remove the metal, rotary evaporate the filtrate, pass through a column, rotary evaporate the mixture, add trifluoroacetic acid to form a salt of the product, and filter to obtain the product Ligand, which is used as the ligand required for the reaction;

[0017] Step (3): Under a nitrogen atmosphere, mix lithium chloride with a tetrahydrofuran solution at 0 °C, add compound S4 and compound S5 with stirring, and then stir overnight at 60 °C to obtain compound S6;

[0018] Step (4): Under a nitrogen atmosphere, at 0 °C, add Ligand, a metal copper compound, and potassium bis(trimethylsilyl)amide (KHMDS) to toluene, add S6 with stirring, and then add compound S7 at -10 °C and stir for reaction overnight to obtain the chiral hydrosilane compound shown in formula (I);

[0019] The synthetic route of the reaction is as follows:

[0020]

[0021] Wherein Ar1 is a C4 thiophene heterocycle, a C6 phenyl group or a dimethoxy-substituted phenyl group, and Ar2 is a C6 phenyl group or a C7 o-methylphenyl group.

[0022] Ligand is one of the following formulas (L1) to (L4):

[0023]

[0024] Further, in step (1), the molar ratio of compound S1 to compound S2 is 1:2.

[0025] Further, in step (2), the molar ratio of compound S3, zinc powder and trifluoroacetic acid is 1:1:1.5.

[0026] Further, in step (3), the molar ratio of compound S4, compound S5 and lithium chloride is 1:1:2.

[0027] Further, in step (4), the metal copper compound ([Cu]) is selected from one of Cu(ACN)4PF6, CuCl, CuBr, [Cu(I)OTf-Tol]2, Cu(OAc)2, Cu(OTf)2.

[0028] Further, in step (4), the molar ratio of compound S6, compound S7, [Cu], Ligand, and KHMDS is 1:1:0.2:0.2:0.15;

[0029] Method B includes the following steps:

[0030] Step (1): Dissolve compound S1 in water to obtain an S1 solution; dissolve compound S9 in absolute ethanol, and then drop it into the S1 solution (absolute ethanol: water = 60:40 mL). Then heat to 70 °C, carry out reflux stirring for 12 h, add water, place it at 0 °C for 5 h, filter the precipitated white solid to obtain the product, that is, compound S10.

[0031] Step (2): In an N2 atmosphere, dissolve compound S10 in a mixed solution of toluene and acetonitrile (15:150) at 0 °C, then add zinc powder and trifluoroacetic acid, and stir at room temperature for about 24 h. Add triethylamine for acid-base neutralization, filter to remove the metal, spin-dry the filtrate, pass through a column, spin-dry the mixture, add trifluoroacetic acid to form a salt of the product, and filter to obtain the product Ligand, which is used as the ligand required for the reaction.

[0032] Step (3): In an N2 atmosphere, at 0 °C, add Ligand, metal copper compound, cesium carbonate, and SX to toluene, add S6 under stirring, and then add S7 at -10 °C and stir to react overnight to obtain the chiral hydrosilane compound shown in formula (I); where SX is (CH3)3COOCHBr(CH3)2;

[0033] The synthetic route of the reaction is as follows:

[0034]

[0035] Where Ar1 is a C6 phenyl or a dimethoxy-substituted phenyl, and Ar2 is a C6 phenyl.

[0036] The ligand is one of the following formulas (L1) or (L4):

[0037]

[0038] Furthermore, in step (1), the molar ratio of compound S1 to compound S9 is 1:2.

[0039] Furthermore, in step (2), the molar ratio of compound S10, zinc powder, and trifluoroacetic acid is 1:1:1.5.

[0040] Furthermore, in step (3), the metal copper compound ([Cu]) is Cu(ACN)4PF 6， one of CuCl and CuBr;

[0041] Furthermore, in step (3), the molar ratio of compound S6, compound S7, SX, cesium carbonate, [Cu], and Ligand is 1:1:0.1:2:0.2:0.2.

[0042] The third object of the present invention is to provide the application of the above chiral hydrosilane compound in the transition metal-catalyzed conversion into a compound containing a chiral silicon center, and the following compounds can be synthesized by modification:

[0043]

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] The present invention provides two simple and rapid synthesis methods for chiral hydrosilane compounds, as well as the application of the synthesized chiral hydrosilane compounds.

[0046] In the above method A, starting from cheap and easily available silanes, the synthesis of tert-butyl and methoxyphenylsilanes is achieved through Grignard reagent reactions. In the copper-catalyzed reaction system, KHMDS reacts with FeiPhos to synthesize chiral hydrosilane compounds, reducing the reaction cost. In the above method B, cesium carbonate and bromo compounds are added during the metal copper-catalyzed reaction process to obtain the corresponding chiral hydrosilane compounds. In terms of the product range, it is difficult to prepare relatively complex chiral hydrosilane compound substrates in existing similar substrates, and the existing palladium-catalyzed system has a high cost. The construction of these methods also means that more abundant and complex functional groups can be introduced into the structure, greatly broadening the product range and laying a foundation for subsequent application transformation. Description of the Drawings

[0047] Figure 1 1H NMR spectrum of the chiral hydrosilane compound Ia prepared in Example 1.

[0048] Figure 2In a, it is the liquid chromatography diagram of racemic hydrosilane, and in b, it is the liquid chromatography diagram of the chiral hydrosilane compound Ia prepared in Example 1. Detailed implementation mode

[0049] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments. Unless otherwise specified, the raw materials used in the embodiments can be purchased commercially or prepared by conventional methods.

[0050] The compounds shown in formula (I) are prepared by the following general methods in the embodiments of the present invention, including Method A and Method B; wherein Method A:

[0051]

[0052] Wherein Ar1 is a C4 thiophene heterocycle, a C6 phenyl group or a dimethoxy-substituted phenyl group, and Ar2 is a C6 phenyl group or a C7 o-methylphenyl group.

[0053] Ligand is one of the following formulas (L1) to (L4):

[0054]

[0055] In a dry flask equipped with a magnetic stir bar and a rubber septum, dissolve S2 (2 equivalents) in absolute ethanol, and add it to a solution of S1 (1 equivalent) (absolute ethanol: water = 60:40 mL). The addition is carried out dropwise for about 1 h, then heated to 70 °C, and after reflux stirring, 30 mL of water is added. After standing at 0 °C for 5 h, a white solid precipitates and is filtered by suction. It is washed 3 times each with cold ethanol and cold deionized water, and the product is dried by suction to obtain S3.

[0056] Dissolve S3 (1 equivalent) in a mixed solvent of toluene and acetonitrile (15:150). Add zinc powder to a dry flask equipped with a magnetic stir bar and a rubber septum, add the above toluene-acetonitrile mixed solution, and slowly add trifluoroacetic acid (1.5 equivalents) at 0 °C, and then stir at room temperature for about 24 h. After the 24 h stirring reaction is completed, add triethylamine for acid-base neutralization, filter off the metal, rotary evaporate the filtrate, pass through a column, rotary evaporate the mixture, add trifluoroacetic acid to form a salt of the product, and filter to obtain the product Ligand.

[0057]

[0058] Add a solution of lithium chloride and tetrahydrofuran to a dry flask equipped with a magnetic stir bar, add S4 (1 equivalent) and S5 (1 equivalent) under stirring, and then stir at 60 °C overnight to obtain compound S6.

[0059] Add ligand (0.2 eq), metal copper compound (0.2 eq), and KHMDS (0.15 eq) to a dry flask equipped with a magnetic stir bar and a rubber septum, mix with toluene, add S6 (1 eq) with stirring, and then add S7 (1 eq) at -10 °C and stir overnight to obtain Compound I.

[0060] Method B:

[0061]

[0062] Wherein Ar1 is a C6 phenyl or dimethoxy-substituted phenyl, and Ar2 is a C6 phenyl.

[0063] Ligand is one of the following formulas (L1) or (L4):

[0064]

[0065] In a dry flask equipped with a magnetic stir bar and a rubber septum, dissolve S9 (2 eq) in absolute ethanol, add the solution of S1 (1 eq) (absolute ethanol: water = 60:40 mL), and add dropwise for about 1 h. Then heat to 70 °C, carry out reflux stirring, add 30 mL of water, place at 0 °C for 5 h, filter after white solid precipitates, wash with cold ethanol and cold deionized water 3 times each, and dry the product by suction to obtain S10.

[0066] Dissolve S10 (1 eq) in a mixed solvent of toluene and acetonitrile (15:150). Add zinc powder to a dry flask equipped with a magnetic stir bar and a rubber septum, add the above toluene-acetonitrile mixed solution, slowly add trifluoroacetic acid (1.5 eq) at 0 °C, and then stir at room temperature for about 24 h. After the 24 h stirring reaction is complete, add triethylamine for acid-base neutralization, filter off the metal, evaporate the filtrate to dryness, pass through a column, evaporate the resulting mixture to dryness, add trifluoroacetic acid to form a salt of the product, and filter to obtain the product Ligand.

[0067]

[0068] Add ligand (0.2 eq), metal copper compound (0.2 eq), cesium carbonate (2 eq), and SX (0.1 eq) to a dry flask equipped with a magnetic stir bar and a rubber septum, mix with toluene, add S6 (1 eq) with stirring, and then add (1 eq) at -10 °C and stir overnight to obtain Compound I;

[0069] The present invention will be further described below.

[0070] Example 1

[0071]

[0072] Preparation of Compound Ia: It can be prepared according to Method A or B in the general method. Any of L1 to L4 can be used as the Ligand for the reaction. 0.049 g of Compound Ia was obtained by silica gel column chromatography with a yield of 90%, which is a colorless oil. 1 H NMR(600MHz,CDCl3)δ7.60 - 7.58(m,2H),7.44 - 7.41(m,1H),7.39 - 7.36(m,2H),7.32(d,J=4.2Hz,4H),7.26 - 7.24(m,1H),4.81 - 4.76(m,3H),1.00(s,9H). 13 C NMR(151MHz,CDCl3)δ140.71,134.71,133.63,130.19,128.37,127.95,127.23,126.43,66.90,25.82,18.26.HRMS(ESI,m / z)calcd for C 17 H 23 OSi[M+Na] + :271.1513,found:271.1519.

[0073] The 1H NMR spectrum of Compound Ia is as Figure 1 shown.

[0074] The liquid phase spectrum of Compound Ia is as Figure 2 shown.

[0075] Example 2

[0076]

[0077] Preparation of Compound Ib: It was prepared according to Method A in the general method. L1 was used as the Ligand. 0.052 g of Compound Ib was obtained by silica gel column chromatography with a yield of 92%, which is a colorless oil. 1 HNMR(600MHz,CDCl3)δ7.59(dd,J=7.8,1.2Hz,2H),7.43 - 7.40(m,1H),7.38 - 7.36(m,2H),7.20(d,J=7.8Hz,2H),7.13(d,J=7.8Hz,2H),4.80 - 4.71(m,3H),2.33(s,3H),0.98(s,9H). 1313C NMR (151 MHz, CDCl3) δ 137.68, 136.84, 134.72, 133.72, 130.14, 129.05, 127.92, 126.58, 66.84, 25.82, 21.28, 18.24. HRMS did not ionize using ESI and APCI.

[0078] Example 3

[0079]

[0080] Compound Ic was prepared: Prepared according to Method A in the general method, using L1 as the Ligand. 0.042 g of Compound Ic was obtained by silica gel column chromatography, with a yield of 62%, as a colorless oil. 1 1H NMR (600 MHz, CDCl3) δ 7.59–7.57 (m, 4H), 7.45 - 7.42 (m, 3H), 7.38 (t, J = 7.2 Hz, 2H), 4.85 - 4.80 (m, 2H), 4.77 (s, 1H), 1.01 (s, 9H). 13 13C NMR (151 MHz, CDCl3) δ 144.77, 134.66, 133.20, 130.40, 129.48 (q, JCF = 32.4 Hz), 128.07, 126.41, 125.35 (q, JCF = 3.3 Hz), 124.44 (q, JCF = 270.8 Hz), 66.22, 25.77, 18.27. 19 19F NMR (565 MHz, CDCl3) δ -62.38. HRMS did not ionize using ESI and APCI.

[0081] Example 4

[0082]

[0083] Compound Id was prepared: Prepared according to Method A in the general method, using L1 as the Ligand. 0.032 g of Compound Id was obtained by silica gel column chromatography, with a yield of 46%, as a yellow oil. 1 1H NMR (600 MHz, CDCl3) δ 7.64 - 7.53 (m, 2H), 7.39 - 7.36 (m, 2H), 7.32 (d, J = 4.2 Hz, 4H), 7.26 - 7.24 (m, 1H), 4.81 - 4.76 (m, 3H), 1.00 (s, 9H). 1313C NMR (151 MHz, CDCl3) δ 140.71, 134.71, 133.63, 130.19, 128.37, 127.95, 127.23, 126.43, 66.90, 25.82, 18.26. HRMS (ESI, m / z) calcd for C 17 H 23 OSi [M+Na] + : 271.1513, found: 348.105.

[0084] Example 5

[0085]

[0086] Preparation of Compound Ie: Prepared according to Method A in the general method, using L1 as the ligand. 0.040 g of Compound Ie was obtained by silica gel column chromatography with a yield of 57%, as a yellow oil. 1 1H NMR (600 MHz, CDCl3) δ 7.59 - 7.52 (m, 2H), 7.43 - 7.41 (m, 1H), 7.39 - 7.36 (m, 1H), 7.32 (d, J = 4.2 Hz, 4H), 7.26 - 7.24 (m, 1H), 4.81 - 4.76 (m, 3H), 1.00 (s, 9H). 13 13C NMR (151 MHz, CDCl3) δ 140.71, 134.71, 133.63, 130.19, 128.37, 127.95, 127.23, 126.43, 66.90, 25.82, 18.26. HRMS (ESI, m / z) calcd for C 17 H 23 OSi [M+Na] + : 348.1058, found: 348.1053.

[0087] Example 6

[0088]

[0089] Preparation of Compound If: Prepared according to Method A in the general method, using L1 as the ligand. 0.034 g of Compound If was obtained by silica gel column chromatography with a yield of 49%, as a yellow oil. 1HNMR(600MHz,CDCl3)δ7.64 - 7.52(m,2H),7.41 - 7.40(m,1H),7.39 - 7.36(m,1H),7.32(d,J=4.2Hz,4H),7.26 - 7.24(m,1H),4.81–4.76(m,3H),1.00(s,9H). 13 C NMR(151MHz,CDCl3)δ140.71,134.71,133.63,130.19,128.37,127.95,127.23,126.43,66.90,25.82,18.26.HRMS(ESI,m / z)calcd for C 17 H 23 OSi[M+Na] + :348.1058,found:348.1053.

[0090] Example 7

[0091]

[0092] Compound Ig was prepared according to Method A in the general method. Ligand L1 was used. 0.050 g of compound Ig was obtained by silica gel column chromatography with a yield of 90%, which was a yellow oil. 1 H NMR(400MHz,CDCl3)δ7.65 - 7.59(m,2H),7.45 - 7.35(m,3H),7.23(dd,J=5.1,1.2Hz,1H),6.93 - 6.91(m,1H),6.88 - 6.87(m,1H),4.95 - 4.87(m,2H),4.74(s,1H),0.97(s,9H). 13 C NMR(101MHz,CDCl3)δ144.12,134.72,133.42,130.25,127.96,126.63,125.04,124.58,62.42,25.73,18.15.HRMS(ESI,m / z)calcd for C 15 H 21 OSSi[M+Na] + :277.1077,found:277.1076.

[0093] Example 8

[0094]

[0095] Preparation of Compound Ih: Prepared according to Method A in the general method, with Ligand being L1. 0.047 g of Compound Ih was obtained by silica gel column chromatography, with a yield of 90%, as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.58 - 7.56 (m, 2H), 7.42 - 7.34 (m, 4H), 6.28 (dd, J = 3.1, 1.9 Hz, 1H), 6.19 (d, J = 2.9 Hz, 1H), 4.72 - 4.65 (m, 3H), 0.95 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 153.67, 142.38, 134.68, 133.57, 130.13, 127.88, 110.27, 107.96, 59.86, 25.73, 18.17. HRMS (ESI, m / z) calcd for C 15 H 21 O2Si [M+Na] + : 261.1305, found: 261.1308.

[0096] Example 9

[0097]

[0098] Preparation of Compound Ii: Prepared according to Method A in the general method, with Ligand being L1. 0.046 g of Compound Ii was obtained by silica gel column chromatography, with a yield of 72%, as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.82 - 7.76 (m, 4H), 7.63 - 7.60 (m, 2H), 7.48 - 7.36 (m, 6H), 4.97 - 4.90 (m, 2H), 4.80 (s, 1H), 1.02 (s, 9H). 13C NMR (101 MHz, CDCl3) δ 138.16, 134.74, 134.25, 133.61, 133.47, 132.92, 130.23, 128.07, 128.03, 127.97, 127.82, 126.11, 125.74, 124.96, 67.11, 25.85, 18.30. HRMS (ESI, m / z) calcd for C 21 H 25 OSi [M+Na] + : 321.1669, found: 321.1661.

[0099] Example 10

[0100]

[0101] Preparation of Compound Ij: Prepared according to Method A in the general method, with Ligand being L1. 0.023 g of Compound Ii was obtained by silica gel column chromatography, with a yield of 32%, as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ 8.42 - 8.33 (m, 1H), 8.31 - 8.20 (m, 2H), 8.0 (m, 2H), 7.53 - 7.42 (m, 5H), 7.27 (m, 3H), 7.18 (m, 2H), 5.23 (s, 1H), 0.99 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 133.24, 129.31, 128.11, 131.02, 132.55, 126.64, 132.53, 125.87, 128.30, 129.52, 125.61, 125.66, 125.48, 125.91, 130.04, 20.01, 67.12, 26.71, 26.75, 26.72. HRMS (APCI, m / z) calcd for C25H 26 OSi[M + Na] + : 370.1822, found: 370.1823.

[0102] Example 11

[0103]

[0104] Preparation of Compound Ik: Prepared according to Method A in the general method, with Ligand being L1. 0.060 g of Compound Ii was obtained by silica gel column chromatography, with a yield of 87%, as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.38 (m, 4H), 7.27 (m, 7H), 7.24 - 7.15 (m, 4H), 6.16 (s, 1H), 0.99 (s, 9H). HRMS (APCI, m / z) calcd for C 23 H 26 OSi[M + Na] + : 346.1434, found: 346.1437.

[0105] Example 12

[0106]

[0107] Preparation of Compound Il: Prepared according to Method A in the general method, with Ligand being L1. 0.040 g of Compound Il was obtained by silica gel column chromatography, with a yield of 62%, as a colorless oil.1 H NMR (600 MHz, CDCl3) δ 7.60 - 7.58 (m, 2H), 7.44 - 7.41 (m, 1H), 7.39 - 7.36 (m, 2H), 7.32 (d, J = 4.2 Hz, 4H), 7.29 (m, 1H), 7.26 - 7.14 (m, 4H), 4.81 - 4.76 (m, 3H), 3.21 (s, 3H). HRMS (ESI, m / z) calcd for C 20 H 20 O2Si [M + Na] + : 320.1513, found: 320.1515.

[0108] Example 13

[0109]

[0110] Preparation of Compound Im: Prepared according to Method A in the general method, using Ligand L1. 0.045 g of Compound Im was obtained by silica gel column chromatography with a yield of 69%, as a yellow oil. 1 H NMR (400 MHz, CDCl3) δ 7.60 - 7.58 (m, 4H), 7.45 - 7.35 (m, 6H), 7.23 (dd, J = 5.1, 1.2 Hz, 2H), 6.93 - 6.91 (m, 2H), 6.88 - 6.87 (m, 2H), 4.95 - 4.87 (m, 2H), 4.74 (s, 1H), 3.19 (s, 3H). HRMS (ESI, m / z) calcd for C 18 H 18 OSSi [M + Na] + : 326.0877, found: 326.0876.

[0111] Example 14

[0112]

[0113] Preparation of Compound In: Prepared according to Method A in the general method, using Ligand L1. 0.045 g of Compound In was obtained by silica gel column chromatography with a yield of 74%, as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.58 - 7.56 (m, 2H), 7.42 - 7.34 (m, 6H), 6.28 (dd, J = 3.1, 1.9 Hz, 2H), 6.19 (d, J = 2.9 Hz, 2H), 4.72 - 4.65 (m, 3H), 3.23 (s, 3H). HRMS (ESI, m / z) calcd for C18 H 18 O3Si[M + Na] + : 310.1025, found: 310.1028.

[0114] Example 15

[0115]

[0116] Preparation of Compound Io: Prepared according to Method A in the general method, using Ligand L1. 0.028 g of Compound Io was obtained by silica gel column chromatography with a yield of 36%, which was a yellow oil. 1 H NMR(600 MHz, CDCl3) δ 7.60 - 7.58(m, 2H), 7.39 - 7.36(m, 5H), 7.32(d, J = 4.2 Hz, 4H), 7.26 - 7.24(m, 2H), 4.81 - 4.76(m, 3H), 3.22(s, 3H) HRMS(ESI, m / z) calcd for C 20 H 19 O2BrSi[M + Na] + : 398.0313, found: 398.0319.

[0117] Example 16

[0118]

[0119] Preparation of Compound Ip: Prepared according to Method A in the general method, using Ligand L1. 0.052 g of Compound Ip was obtained by silica gel column chromatography with a yield of 66%, which was a yellow oil. 1 HNMR(600 MHz, CDCl3) δ 7.60 - 7.58(m, 2H), 7.44 - 7.41(m, 1H), 7.38 - 7.35(m, 3H), 7.32(d, J = 4.2 Hz, 4H), 7.26 - 7.24(m, 2H), 4.81 - 4.76(m, 3H), 3.51(s, 3H).

[0120] HRMS(ESI, m / z) calcd for C 20 H 19 O2BrSi[M + Na] + : 398.1218, found: 398.1213.

[0121] Example 17

[0122]

[0123] Preparation of Compound Iq: Prepared according to Method A in the general method, with Ligand being L1. 0.038 g of Compound Iq was obtained by silica gel column chromatography, with a yield of 48%, as a yellow oil. 1 HNMR(600MHz,CDCl3)δ7.60 - 7.58(m,2H),7.44 - 7.41(m,1H),7.39 - 7.36(m,4H),7.32(d,J=4.2Hz,4H),7.26 - 7.24(m,2H),4.81 - 4.76(m,3H),3.09(s,3H).HRMS(ESI,m / z)calcd for C 20 H 19 O2BrSi[M+Na] + :398.1321,found:398.1323.

[0124] Example 18

[0125]

[0126] Preparation of Compound Ir: Prepared according to Method A in the general method, with Ligand being L1. 0.033 g of Compound Ir was obtained by silica gel column chromatography, with a yield of 41%, as a colorless oil. 1 H NMR(600MHz,CDCl3)δ7.38(m,4H),7.30 - 7.28(m,8H),7.24 - 7.15(m,6H),6.94(s,1H),6.16(s,1H),3.86(s,3H).HRMS(ESI,m / z)calcd for C 26 H 24 O2Si[M+Na] + :396.1033,found:396.1041.

[0127] The above description of the present invention is illustrative rather than restrictive. Those skilled in the art understand that many modifications, variations or equivalents can be made within the spirit and scope defined by the claims, but they will all fall within the protection scope of the present invention.

Claims

1. A chiral hydrosilane compound, characterized in that, The structure is as shown in formula (I): In the formula, * represents a chiral silicon atom; R1 is one of tert-butyl and o-methoxyphenyl; R2 is C 6-14 aryl, C5 heterocycle, C 13 one of diphenylmethane.

2. The chiral hydrosilane compound according to claim 1, wherein The structural formula of the chiral hydrosilane compound is selected from one of the following formulas (Ia) to (Ir):

3. A method for preparing a chiral hydrosilane compound according to any one of claims 1-2, characterized in that, The preparation method includes the following steps: Step (1): Dissolve compound S1 in water to obtain an S1 solution, dissolve compound S2 in absolute ethanol and then drop it into the S1 solution, heat to 70 °C, carry out reflux stirring for 12 h, then add water, place it at 0 °C for 5 h, filter with suction after white solid precipitates to obtain the product, that is, compound S3; Step (2): Mix compound S3 with zinc powder and trifluoroacetic acid at 0 °C, stir and react at room temperature for 24 h, and carry out post-treatment to obtain the product Ligand, which is used as the ligand required for the reaction; Step (3): Stir and mix lithium chloride, compound S4 and compound S5 at 0 °C, and then stir overnight at 60 °C to obtain compound S6; Step (4): Mix Ligand, metal copper compound and KHMDS in toluene, add S6 under stirring, and then add compound S7 at -10 °C and stir and react overnight to obtain the chiral hydrosilane compound shown in formula (I); The synthetic route of the reaction is as follows: Wherein Ar1 is a C4 thiophene heterocycle, a C6 phenyl group or a dimethoxy-substituted phenyl group, and Ar2 is a C6 phenyl group or a C7 o-methylphenyl group.

4. The preparation method according to claim 3, characterized in that, In step (1), the molar ratio of compound S1 to compound S2 is 1:2; in step (2), the molar ratio of compound S3, zinc powder and trifluoroacetic acid is 1:1:1.5; in step (3), the molar ratio of compound S4, compound S5 and lithium chloride is 1:1:2; in step (4), the molar ratio of compound S6, compound S7, metal copper compound, Ligand, KHMDS is 1:1:0.2:0.2:0.

15.

5. The preparation method according to claim 3, characterized in that, The Ligand is one of the following formulas (L1) to (L4):

6. A method for preparing a chiral hydrosilane compound according to any one of claims 1-2, characterized in that, The preparation method includes the following steps: Step (1): Dissolve compound S1 in water to obtain an S1 solution, dissolve compound S9 in absolute ethanol and then drop it into the S1 solution, heat to 70 °C, carry out reflux stirring for 12 h, then add water, place it at 0 °C for 5 h, filter with suction after white solid precipitates to obtain the product, that is, compound S10; Step (2): Mix compound S10 with zinc powder and trifluoroacetic acid at 0 °C, stir and react at room temperature for 24 h, and carry out post-treatment to obtain the product Ligand, which is used as the ligand required for the reaction; Step (3): Mix Ligand, metal copper compound, cesium carbonate and SX in toluene, add compound S6 under stirring, and then add compound S7 at -10 °C and stir and react overnight to obtain the chiral hydrosilane compound shown in formula (I); wherein, SX is (CH3)3COOCHBr(CH3)2; The synthetic route of the reaction is as follows: Wherein Ar1 is a C6 phenyl group or a dimethoxy-substituted phenyl group, and Ar2 is a C6 phenyl group.

7. The preparation method according to claim 6, characterized in that, In step (1), the molar ratio of compound S1 to compound S9 is 1:2; in step (2), the molar ratio of compound S10, zinc powder and trifluoroacetic acid is 1:1:1.5; in step (3), the molar ratio of compound S6, compound S7, SX, cesium carbonate, metal copper compound, and Ligand is 1:1:0.1:2:0.2:0.

2.

8. The preparation method according to claim 6, characterized in that, Ligand is selected from one of the following formulas (L1) or (L4):

9. Use of the chiral hydrosilane compound according to any one of claims 1-2 in the transition metal-catalyzed conversion to a compound containing a chiral silicon center.

Images