Preparation method of six-membered cyclic chiral double-silicon compound

Abstract

The invention discloses a preparation method of a six-membered cyclic chiral double-silicon compound, which comprises the following steps: under the protection of nitrogen, taking 1, 3-conjugated diene and dichlorodisilane as raw materials, and carrying out cyclization reaction in a solvent system in the presence of a nickel catalyst, lewis acid, a ligand and a reducing agent; after the reaction is finished, cooling to room temperature, adding ethyl acetate for dilution, extracting by using a saturated potassium sodium tartrate solution and ethyl acetate, drying an organic phase, and carrying out column chromatography to obtain a target product. According to the synthesis method, a one-step method is adopted, and synthesis of the chiral six-membered ring double-silicon compound is achieved under the combined action of the ligand and the nickel catalyst. The system is simple, and a target product can be obtained without additional treatment. The method is easy to operate, wide in substrate applicability and high in atom economy, and is superior to a traditional synthesis method in multiple aspects. The invention provides a new synthesis means for the chiral double-silicon compound, and has atom economy and industrial application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing a six-membered cyclic chiral disilic compound. Background Art

[0002] Chiral organosilicon compounds have a wide range of applications in organic synthesis, silicon-based materials science, and medicinal chemistry. Chiral disilicon compounds with silicon or carbon stereocenters have attracted much attention due to their potential as chiral organosilicon synthons. Disilicon compounds have a unique nonpolar Si-Si bond (220-300 kJ-mol -1 ), can construct C-Si bonds through transition metal-catalyzed Si-Si bond activation, and is therefore considered an efficient silylation agent. In addition, due to the unique electronic and luminescent properties produced by the σ conjugation of Si-Si bonds, chiral disilicon compounds have great application potential in the field of materials science.

[0003] Despite the growing interest in chiral disilic chemistry, the number of available disilic compounds is still limited and the synthesis strategies are still lacking. A common synthesis method is to react aryl lithium or magnesium reagents with silicon electrophiles, but this method usually has problems with poor tolerance of functional groups and the inability to control chirality. The structures of disilic compounds that have been reported as silylating agents are as follows (I. Beletskaya, C. Moberg, Chem. Rev.2006, 106, 2320-2354.):

[0004]

[0005] The above-mentioned disilic reagents have simple structures and lack of diversity, which greatly limits the application range of disilic reagents. Therefore, it is very necessary to develop a simple and efficient method to synthesize chiral disilic compounds containing carbon chiral centers as new chiral silylating reagents. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a six-membered cyclic chiral disilic compound, by which a conjugated diene is migrated and inserted into an allyl nickel intermediate by a nickel silicon intermediate, and an intramolecular electrophilic addition reaction is further carried out, thereby successfully introducing a Si-Si bond into different compound skeletons, thereby overcoming the above-mentioned defects of the prior art.

[0007] The method for preparing the six-membered cyclic chiral disilic compound of the present invention adopts a one-step method to prepare the target product, comprising the following steps:

[0008] Under nitrogen protection, 1,3-conjugated diene and dichlorodisilane are used as raw materials, and a cyclization reaction is carried out in a solvent system in the presence of a nickel catalyst, a Lewis acid, a ligand and a reducing agent; after the reaction is completed and cooled to room temperature, ethyl acetate is added to dilute, and the mixture is extracted with a saturated potassium sodium tartrate solution and ethyl acetate. After the organic phase is dried, the target product is obtained by column chromatography.

[0009] The reaction route is as follows:

[0010]

[0011] Wherein the substituents R and R 1 , R 2 Each is independently selected from alkyl, substituted alkyl, aryl substituted aryl or hydrogen.

[0012] The alkyl group includes a linear alkyl group, a branched alkyl group or a cyclic alkyl group.

[0013] The substituents include one or more of alkyl, alkoxy, halogen, heteroatom (N, O, S, etc.) and the like.

[0014] The nickel catalyst is nickel (II) trifluoromethanesulfonate; the Lewis acid is trimethylaluminum; and the reducing agent is manganese powder.

[0015] The ligand is a combination of a chiral bidentate organophosphorus ligand (ligand 1) and a non-chiral bidentate nitrogen ligand (ligand 2). The ligand 1 is (R)-(-)-1-[(S)-2-diphenylphosphoferrocene]ethyl-di-tert-butylphosphine, and the ligand 2 is 2,2'-bipyridine.

[0016] The solvent is a mixture of 1,3-dimethyl-2-imidazolidinone and n-hexane, and the volume ratio of the two is 1:20 to 1:2.

[0017] During the reaction, the molar ratio of 1,3-conjugated diene to dichlorodisilane is 1:2.

[0018] The molar ratio of 1,3-conjugated diene to nickel catalyst is controlled to be 1:0.05~1:0.20.

[0019] The molar ratio of 1,3-conjugated diene to Lewis acid is controlled to be 1:0.5~1:4.

[0020] The molar ratio of 1,3-conjugated diene to reducing agent is controlled to be 1:0.5~1:4.

[0021] The molar ratio of 1,3-conjugated diene to ligand 1 is controlled to be 1:0.05-1:0.20, and the molar ratio of 1,3-conjugated diene to ligand 2 is controlled to be 1:0.05-1:0.20.

[0022] The cyclization reaction temperature is 30-70°C and the reaction time is 4-15 h.

[0023] The structural formula of the six-membered cyclic chiral disilic compound prepared by the method of the present invention includes the following:

[0024]

[0025] The synthesis method of the present invention adopts a one-step method, and under the joint action of a ligand and a nickel catalyst, the synthesis of a chiral six-membered cyclic disilic compound is achieved. The product can be used as a new chiral organosilicon synthon, and the chirality can be maintained during subsequent transformations. The reaction system is simple, and the target product can be obtained without additional treatment. The method is easy to operate, has a wide substrate applicability, and has high atom economy, and is superior to traditional synthesis methods in many aspects. The present invention provides a new synthesis method for chiral disilic compounds, which has atom economy and industrial application prospects. DETAILED DESCRIPTION

[0026] Substrate synthesis route:

[0027]

[0028] Prepare a 250 mL round-bottom flask and add a suitable magnet. First, add 1.5 equivalents of methyltriphenylphosphonium bromide, purge with nitrogen three times on a double-row tube, and add THF. Then place the flask in an ice-water bath at 0°C, add NaHMDS (1.6 equiv) dropwise, and the resulting suspension continues to react at this temperature for 30 minutes. Then, cinnamaldehyde is added dropwise to the above solution and detected by TLC until the reaction is complete. After the reaction is completed, the corresponding 1,3-conjugated diene product is obtained by filtration, extraction, drying, concentration, and column chromatography separation and purification.

[0029] Product transformation:

[0030]

[0031] Prepare a 10 mL round-bottom flask, add 3g (0.2 mmol) of white solid, without adding a magnet. Place in air at 35°C for five days. At the end of the reaction, it can be found that the white solid 3g has completely transformed into a colorless oily liquid 4g. The colorless oily liquid is separated by column chromatography to obtain a product 4g with a yield of 85% and an enantiomeric excess of 92%.

[0032] Example 1: Preparation of (S)-1,1,2,2-tetramethyl-3-phenyl-1,2,3,6-tetrahydro-1,2-disilazine

[0033]

[0034] Under nitrogen protection, 1a (0.2 mmol), chlorosilane 2 (0.4 mmol), nickel (II) trifluoromethanesulfonate (0.02 mmol), 2,2'-bipyridine (0.02 mmol), chiral bisphosphine ligand (R)-(-)-1-[(S)-2-diphenylphosphinopheno]ethyl-di-tert-butylphosphine (0.02 mmol), trimethylaluminum (0.4 mmol), manganese powder (0.6 mmol), n-hexane (0.8 mL), 1,3-dimethyl-2-imidazolidinone (0.4 mL) were added to a 10 mL Shrek tube in sequence. After the addition was completed, the mixture was stirred at 50 °C for 12 h. After the reaction was completed and cooled to room temperature, a saturated solution of potassium sodium tartrate and ethyl acetate were added for extraction. The obtained organic phase was dried and the solvent was removed using a rotary evaporator. The residue was separated by column chromatography to obtain the product 3a with a yield of 78% and an enantiomeric excess of 92%, as a colorless oily liquid.

[0035] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1 H NMR (400 MHz, CDCl3) δ 7.30-7.28 (m, 2H), 7.11 (ddt, J = 7.9, 7.1, 1.3 Hz, 1H), 7.06-7.04(m, 2H), 5.88-5.83 (m, 1H), 5.74-5.67 (m, 1H), 2.93 (dt, J = 4.8, 2.3 Hz,1H), 1.68 (dd, J = 13.7, 8.9 Hz, 1H), 1.41-1.36 (m, 1H), 0.20 (s, 3H), 0.09(s, 3H), -0.03 (s, 3H), -0.14 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 142.7, 130.4,128.3, 127.0, 124.3, 124.3, 38.3, 17.3, -3.3, -3.5, -4.9, -6.1.HRMS (ESI) (m / z): Calcd for C 14 H 22 Si2 [M+H] +: 247.1338, found: 247.1326. It is proved that the colorless oily liquid product obtained in the above reaction is (S)-1,1,2,2-tetramethyl-3-phenyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0036] Example 2: Preparation of (S)-1,1,2,2-tetramethyl-3-p-methylphenyl-1,2,3,6-tetrahydro-1,2-disilazine

[0037]

[0038] 1b and 2 were used as the starting substrates for the reaction to prepare the target product 3b, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 58% and an enantiomeric excess of 96%.

[0039] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1 H NMR (500 MHz, CDCl3) δ 7.08 (d, J = 7.8 Hz, 2H), 6.94 (d, J = 8.0 Hz, 2H), 5.84-5.81 (m,1H), 5.71-5.65 (m, 1H), 2.92- 2.85 (m, 1H), 2.31 (s, 3H), 1.67 (dd, J = 13.7,8.9 Hz, 1H), 1.39- 1.34 (m, 1H), 0.19 (s, 3H), 0.08 (s, 3H), -0.03 (s, 3H), -0.14 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 139.6, 133.6, 130.7, 129.0, 127.0,124.1, 37.8, 21.1, 17.3, -3.3, -3.5, -4.9, -6.1. HRMS (ESI) (m / z): Calcd forC 15 H 24 Si2 [M+H] + : 261.1495, found: 261.1481. It is proved that the colorless oily liquid product obtained in the above reaction is (S)-1,1,2,2-tetramethyl-3-p-methylphenyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0040] Example 3: Preparation of (S)-3-(4-isopropylphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0041]

[0042] 1c and 2 were used as starting substrates to prepare the target product 3c, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 66% and an enantiomeric excess of 94%.

[0043] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1 H NMR (400 MHz, CDCl3) δ 7.16-7.14 (m, 2H), 7.00-6.98 (m, 2H), 5.89-5.84 (m, 1H), 5.73-5.66 (m, 1H), 2.93-2.86 (m, 2H), 1.72-1.66 (m, 1H), 1.42- 1.37 (m, 1H), 1.27 (d, J= 7.0 Hz, 6H), 0.21 (s, 3H), 0.11 (s, 3H), 0.00 (s, 3H), -0.10 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 144.6, 139.9, 130.8, 127.0, 126.3, 124.0, 37.8, 33.7, 24.3,17.3, -3.3, -3.5, -4.8, -6.0.HRMS (ESI) (m / z): Calcd for C 17 H 29 Si2 [M+H] + :289.1808, found: 289.1813. It is proved that the colorless oily liquid product obtained in the above reaction is (S)-3-(4-isopropylphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0044] Example 4: Preparation of (S)-3-(4-tert-butylphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0045]

[0046] 1d and 2 were used as starting substrates to prepare the target product 3d, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 53% and an enantiomeric excess of 95%.

[0047] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1 H NMR (400 MHz, CDCl3) δ 7.30-7.26 (m, 2H), 6.99-6.96 (m, 2H), 5.86-5.82 (m, 1H), 5.71-5.64(m, 1H), 2.89 (dt, J = 4.5, 2.2 Hz, 1H), 1.67 (dd, J = 13.7, 8.9 Hz, 1H), 1.40- 1.31 (m, 1H), 1.31 (s, 9H), 0.19 (s, 3H), 0.09 (s, 3H), -0.02 (s, 3H), -0.13 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 146.8, 139.4, 130.7, 126.6, 125.1,123.9, 37.6, 34.4, 31.6, 17.3, -3.3, -3.5, -4.9, -6.1.HRMS (ESI) (m / z): Calcdfor C 18 H 30 Si2 [M+H] + : 303.1964, found: 303.1959. This proves that the white solid product obtained in the above reaction is (S)-3-(4-tert-butylphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0048] Example 5: Preparation of (S)-3-(4-fluorophenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0049]

[0050] 1e and 2 were used as the starting substrates for the reaction to prepare the target product 3e, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 66% and an enantiomeric excess of 90%.

[0051] By hydrogen nuclear magnetic resonance spectroscopy ( 1H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1 H NMR (400 MHz, CDCl3) δ 7.01-6.94 (m, 4H), 5.80-5.76 (m, 1H), 5.73-5.67 (m, 1H), 2.90 (dt, J= 5.6, 2.2 Hz, 1H), 1.69 (dd, J = 13.5, 8.5 Hz, 1H), 1.39- 1.33 (m, 1H), 0.19 (s, 3H), 0.09 (s, 3H), -0.04 (s, 3H), -0.14 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ160.5 (d, J = 242.4 Hz), 138.3 (d, J = 3 Hz), 130.2, 128.0 (d, J = 8 Hz), 124.5, 115.0 (d, J = 21.2 Hz), 37.4, 17.3, -3.4, -3.6, -5.0, -6.2. 19 F NMR (376MHz, CDCl3) δ -120.2. HRMS (ESI) (m / z): Calcd for C 15 H 24 FSi2 [M+H] + : 265.1244,found: 265.1254. It is proved that the colorless oily liquid product obtained in the above reaction is (S)-3-(4-fluorophenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0052] Example 6: Preparation of (S)-3-(4-chlorophenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0053]

[0054] 1f and 2 were used as the starting substrates for the reaction to prepare the target product 3f, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 54% and an enantiomeric excess of 84%.

[0055] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1 H NMR(400 MHz, CDCl3)δ 7.25-7.22 (m, 2H), 6.99-6.95 (m, 2H), 5.80-5.75 (m, 1H), 5.75-5.67 (m, 1H), 2.90 (dt, J = 5.7, 2.1 Hz, 1H), 1.69 (dd, J = 13.7, 8.6 Hz, 1H), 1.39- 1.33(m, 1H), 0.19 (s, 3H), 0.09 (s, 3H), -0.04 (s, 3H), -0.15 (s, 3H). 13 C NMR (101MHz, CDCl3) δ 141.3, 129.8, 129.8, 128.4, 128.1, 124.7, 37.8, -3.4, -3.6, -5.0, -6.2.HRMS (ESI) (m / z): Calcd for C 14 H 21 ClSi2 [M+H] + : 281.0949, found:281.0946. This proves that the colorless oily liquid product obtained in the above reaction is (S)-3-(4-chlorophenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0056] Example 7: Preparation of (S)-3-(4-methoxyphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0057]

[0058] 1g and 2 were used as starting substrates to prepare the target product 3g, and the preparation method was the same as that in Example 1. White solid, product yield 86%, enantiomeric excess 92%.

[0059] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 6.99- 6.95 (m, 2H), 6.86- 6.82 (m, 2H), 5.82- 5.78 (m, 1H), 5.71-5.64 (m, 1H), 3.79 (s, 3H), 2.86 (dt, J = 4.9, 2.2 Hz, 1H), 1.67 (dd, J =13.7, 8.8 Hz, 1H), 1.39- 1.33 (m, 1H), 0.19 (s, 3H), 0.08 (s, 3H), -0.04 (s,3H), -0.14 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 156.8, 134.8, 130.8, 127.8,124.0, 113.8, 55.4, 37.1, 17.3, -3.3, -3.5, -5.0, -6.1. HRMS (ESI) (m / z):Calcd for C 15 H 24 OSi2 [M+H] + : 277.1444, found: 277.1430. This proves that the white solid product obtained in the above reaction is (S)-3-(4-methoxyphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0060] Example 8: Preparation of (S)-3-(Benzo[d][1,3]dioxol-5-yl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0061]

[0062] 1h and 2 were used as starting substrates to prepare the target product 3h, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 68% and an enantiomeric excess of 92%.

[0063] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 6.74 (d, J = 8.0 Hz, 1H), 6.57 (d, J = 1.8 Hz, 1H), 6.49 (dd, J =8.0, 1.8 Hz, 1H), 5.92 (s, 2H), 5.78-5.73 (m, 1H), 5.71- 5.64 (m, 1H), 2.84(dt, J = 4.8, 2.2 Hz, 1H), 1.67 (dd, J = 13.7, 8.7 Hz, 1H), 1.38- 1.32 (m,1H), 0.18 (s, 3H), 0.08 (s, 3H), -0.02 (s, 3H), -0.12 (s, 3H). 13 HRMS (ESI) (m / z): Calcd for C 15 H 22 O2Si2 [M+H] + : 291.1237, found: 291.1226. It is proved that the white solid product obtained in the above reaction is (S)-3-(benzo[d][1,3]dioxol-5-yl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0064] Example 9: Preparation of (S)-3-(3-methoxyphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0065]

[0066] 1i and 2 were used as the starting substrates for the reaction to prepare the target product 3i, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 77% and an enantiomeric excess of 93%.

[0067] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.19 (t, J = 7.9 Hz, 1H), 6.69- 6.65 (m, 2H), 6.62 (t, J = 2.1 Hz, 1H), 5.88- 5.83 (m, 1H), 5.74- 5.67 (m, 1H), 3.81 (s, 3H), 2.92 (dt, J = 5.9,2.2 Hz, 1H), 1.69 (dd, J = 13.7, 8.8 Hz, 1H), 1.41- 1.35 (m, 1H), 0.20 (s,3H), 0.10 (s, 3H), -0.00 (s, 3H), -0.10 (s, 3H). 13 HRMS (ESI) (m / z): Calcd for C 15 H 24 OSi2 [M+H] + : 277.1444,found: 277.1436. It is proved that the colorless oily liquid product obtained in the above reaction is (S)-3-(3-methoxyphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0068] Example 10: Preparation of (S)-N,N-dimethyl-4-(1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazol-3-yl)aniline

[0069]

[0070] 1j and 2 were used as starting substrates to prepare the target product 3j, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 75% and an enantiomeric excess of 87%.

[0071] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (500 MHz, CDCl3) δ 6.98-6.95 (m, 2H), 6.76-6.73 (m, 2H), 5.84-5.81 (m, 1H), 5.70- 5.65(m, 1H), 2.92 (s, 6H), 2.83 (dt, J = 5.8, 2.4 Hz, 1H), 1.67 (dd, J = 13.7,8.9 Hz, 1H), 1.41- 1.35 (m, 1H), 0.19 (s, 3H), 0.10 (s, 3H), -0.01 (s, 3H), -0.11 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 148.1, 131.2, 127.7, 123.7, 113.4,41.3, 36.9, 17.4, -3.3, -3.5, -4.9, -6.0. HRMS (ESI) (m / z): Calcd forC 16 H 27 NSi2 [M+H] + : 290.1760, found: 290.1755. This proves that the white solid product obtained in the above reaction is (S) -N,N-dimethyl-4-(1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazol-3-yl)aniline.

[0072] Example 11: Preparation of (S)-1,1,2,2-tetramethyl-3-(4-methylthiophenyl)-1,2,3,6-tetrahydro-1,2-disilazine

[0073]

[0074] 1k and 2 were used as starting substrates to prepare the target product 3k, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 55% and an enantiomeric excess of 92%.

[0075] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 7.21 (d, J = 8.3 Hz, 2H), 6.98 (d, J = 8.3 Hz, 2H), 5.82- 5.78 (m, 1H),5.73- 5.66 (m, 1H), 2.89 (dt, J = 5.7, 2.2 Hz, 1H), 2.47 (s, 3H), 1.68 (dd, J= 13.7, 8.8 Hz, 1H), 1.39- 1.33 (m, 1H), 0.19 (s, 3H), 0.09 (s, 3H), -0.03(s, 3H), -0.14 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 140.2, 133.2, 130.1, 127.6,127.6, 124.4, 37.9, 17.3, 16.8, -3.3, -3.6, -4.9, -6.1. HRMS (ESI) (m / z): Calcd for C 15 H 24 SSi2 [M+H] + : 293.1215, found: 293.1207. It is proved that the white solid product obtained in the above reaction is (S) -1,1,2,2-tetramethyl-3-(4-methylthiophenyl)-1,2,3,6-tetrahydro-1,2-disilazine.

[0076] Example 12: Preparation of (S)-3-(3,5-dimethoxyphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0077]

[0078] 11 and 2 were used as the starting substrates for the reaction to prepare the target product 31, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 82% and an enantiomeric excess of 97%.

[0079] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 6.25 (t, J = 2.3 Hz, 1H), 6.22 (d, J = 2.2 Hz, 2H), 5.85- 5.80 (m, 1H),5.72- 5.65 (m, 1H), 3.78 (s, 6H), 2.88 (dt, J = 5.7, 2.2 Hz, 1H), 1.68 (dd, J= 13.7, 8.9 Hz, 1H), 1.39- 1.33 (m, 1H), 0.19 (s, 3H), 0.09 (s, 3H), 0.01 (s,3H), -0.09 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 160.7, 145.3, 130.1, 124.2,105.3, 96.4, 55.4, 38.8, 17.3, -3.3, -3.5, -4.7, -5.8. HRMS (ESI) (m / z):Calcd for C 16 H 26 O2Si2 [M+H] + : 307.1550, found: 307.1549. This proves that the white solid product obtained in the above reaction is (S)-3-(3,5-dimethoxyphenyl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0080] Example 13: Preparation of (S)-3-(Furan-2-yl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0081]

[0082] 1m and 2 were used as the starting substrates for the reaction to prepare the target product 3m, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 63% and an enantiomeric excess of 92%.

[0083] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.28 (dd, J = 1.9, 0.9 Hz, 1H), 6.30 (dd, J = 3.2, 1.9 Hz, 1H), 5.89(dt, J = 3.2, 0.8 Hz, 1H), 5.90- 5.66 (m, 2H), 3.04 (d, J = 5.5 Hz, 1H), 1.66 (dd, J = 13.6, 8.4 Hz, 1H), 1.37- 1.31 (m, 1H), 0.18 (s, 3H), 0.14 (s, 3H),0.08 (s, 3H), -0.06 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 157.5, 140.3, 127.5,124.8, 110.4, 102.4, 31.2, 17.3, -3.3, -3.7, -4.2, -5.8. HRMS (ESI) (m / z):Calcd for C 12 H 20 OSi2 [M+H] + : 237.1131, found: 237.1133. This proves that the colorless oily liquid obtained in the above reaction is (S)-3-(furan-2-yl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0084] Example 14: Preparation of (S)-1,1,2,2-tetramethyl-3-(thiophen-2-yl)-1,2,3,6-tetrahydro-1,2-disilazine

[0085]

[0086] 1n and 2 were used as the starting substrates for the reaction to prepare the target product 3n, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 61% and an enantiomeric excess of 91%.

[0087] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.01 (dd, J = 5.2, 1.2 Hz, 1H), 6.94 (dd, J = 5.2, 3.4 Hz, 1H), 6.66(dt, J = 3.5, 1.0 Hz, 1H), 5.79- 5.74 (m, 1H), 5.72- 5.65 (m, 1H), 3.25 (dt,J = 5.0, 1.9 Hz, 1H), 1.67 (dd, J = 13.7, 8.7 Hz, 1H), 1.38- 1.32 (m, 1H),0.19 (s, 3H), 0.09 (s, 6H), -0.05 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 146.7,130.9, 127.1, 124.6, 121.4, 120.8, 33.4, 17.4, -3.3, -3.6, -4.6, -5.9. HRMS(ESI) (m / z): Calcd for C 12 H 20 SSi2 [M+H] + : 253.0902, found: 253.0902. This proves that the colorless oily liquid obtained in the above reaction is (S) -1,1,2,2-tetramethyl-3-(thiophen-2-yl)-1,2,3,6-tetrahydro-1,2-disilazine.

[0088] Example 15: Preparation of (S)-3-([1,1'-biphenyl]-4-yl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine

[0089]

[0090] 1o and 2 were used as the starting substrates for the reaction to prepare the target product 3o, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 78% and an enantiomeric excess of 89%.

[0091] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.63-7.60 (m, 2H), 7.55-7.52 (m, 2H), 7.43 (dd, J = 8.4, 6.9 Hz,2H), 7.34-7.30 (m, 1H), 7.16-7.10 (m, 2H), 5.92-5.87 (m, 1H), 5.77- 5.70 (m,1H), 2.99 (dt, J = 5.7, 2.2 Hz, 1H), 1.71 (dd, J = 13.7, 8.9 Hz, 1H), 1.44-1.38 (m, 1H), 0.22 (s, 3H), 0.12 (s, 3H), 0.02 (s, 3H), -0.09 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 142.0, 141.3, 137.1, 130.2, 128.9, 127.4, 127.0, 127.0,126.9, 124.4, 38.1, 17.3, -3.3, -3.5, -4.8, -6.1. HRMS (ESI) (m / z): Calcd forC 20 H 26 Si2 [M+H] + : 323.1651, found: 323.1647. This proves that the white solid obtained in the above reaction is (S)-3-([1,1'-biphenyl]-4-yl)-1,1,2,2-tetramethyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0092] Example 16: Preparation of (S)-1,1,2,2-tetramethyl-3-(naphthalen-2-yl)-1,2,3,6-tetrahydro-1,2-disilazine

[0093]

[0094] 1p and 2 were used as the starting substrates for the reaction to prepare the target product 3p, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 70% and an enantiomeric excess of 90%.

[0095] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.80-7.74 (m, 3H), 7.47 (s, 1H), 7.45-7.35 (m, 2H), 7.22 (dd, J =8.5, 1.9 Hz, 1H), 6.01- 5.96 (m, 1H), 5.79- 5.72 (m, 1H), 3.11 (dt, J = 5.8,2.2 Hz, 1H), 1.72 (dd, J = 13.8, 8.9 Hz, 1H), 1.46- 1.40 (m, 1H), 0.22 (s,3H), 0.12 (s, 3H), -0.01 (s, 3H), -0.11 (s, 3H). 13 C NMR (101 MHz, CDCl3)140.5, 133.9, 131.3, 130.2, 127.7, 127.6, 127.4, 127.1, 125.9, 124.5, 124.5,124.0, 38.5, 17.3, -3.3, -3.5, -4.8, -6.0. HRMS (ESI) (m / z): Calcd forC 18 H 24 Si2 [M+H] + : 297.1495, found: 297.1492. This proves that the white solid obtained from the above reaction is (S) -1,1,2,2-tetramethyl-3-(naphthalen-2-yl)-1,2,3,6-tetrahydro-1,2-disilazine.

[0096] Example 17: Preparation of (S)-1,1,2,2-tetramethyl-3-(naphthalen-1-yl)-1,2,3,6-tetrahydro-1,2-disilazine

[0097]

[0098] 1q and 2 were used as starting substrates to prepare the target product 3q, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 47% and an enantiomeric excess of 73%.

[0099] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 8.05-8.02 (m, 1H), 7.86-7.82 (m, 1H), 7.64-7.62 (m, 1H), 7.49-7.43(m, 3H), 7.26 (dd, J = 7.1, 1.2 Hz, 1H), 5.96- 5.91 (m, 1H), 5.81- 5.74 (m,1H), 3.90 (dt, J = 5.0, 2.1 Hz, 1H), 1.77 (dd, J = 13.8, 8.9 Hz, 1H), 1.58-1.52 (m, 2H), 0.26 (s, 3H), 0.14 (s, 3H), -0.07 (s, 3H), -0.15 (s, 3H). 13 CNMR (101 MHz, CDCl3) δ 139.6, 134.1, 131.6, 131.5, 129.0, 125.6, 125.4,125.2, 124.8, 124.6, 124.0, 124.0, 32.1, 17.4, -3.2, -3.4, -3.9, -5.4. HRMS(ESI) (m / z): Calcd for C 18 H 24 Si2 [M+H] + : 297.1495, found: 297.1488. This proves that the white solid obtained from the above reaction is (S) -1,1,2,2-tetramethyl-3-(naphthalen-1-yl)-1,2,3,6-tetrahydro-1,2-disilazine.

[0100] Example 18: Preparation of (S)-1,1,2,2,4-pentamethyl-3-phenyl-1,2,3,6-tetrahydro-1,2-disilazine

[0101]

[0102] 1r and 2 were used as the starting substrates for the reaction to prepare the target product 3r, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 40% and an enantiomeric excess of 80%.

[0103] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.26-7.23 (m, 2H), 7.13-7.09 (m, 3H), 5.59 (t, J = 7.1 Hz,1H), 3.04(s, 1H), 1.68-1.67 (m, 3H), 1.52-1.46 (m, 1H), 1.43- 1.37 (m, 1H), 0.13 (s, 3H), 0.12 (s, 3H), 0.04 (s, 3H), 0.03 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ141.4, 135.8, 129.3, 128.1, 124.7, 120.4, 42.0, 26.1, 16.9, -3.3, -3.3, -3.7,-4.1. HRMS (ESI) (m / z): Calcd for C 15 H 24 Si2 [M+H] + : 261.1495, found: 261.1494. It is proved that the colorless oily liquid obtained by the above reaction is (S) -1,1,2,2,4-pentamethyl-3-phenyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0104] Example 19: Preparation of (S)-1,1,2,2,5-pentamethyl-3-phenyl-1,2,3,6-tetrahydro-1,2-disilazine

[0105]

[0106] 1s and 2 were used as the starting substrates for the reaction to prepare the target product 3s, and the preparation method was the same as that in Example 1. The product was a colorless oily liquid with a product yield of 46% and an enantiomeric excess of 99%.

[0107] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 7.29-7.24 (m, 2H), 7.11-7.07 (m, 1H), 7.07-7.03 (m, 2H), 5.59-5.57 (m, 1H), 2.80 (d, J = 5.6 Hz, 1H), 1.80 (t, J = 1.6 Hz, 3H), 1.57- 1.48 (m, 2H), 0.19(s, 3H), 0.08 (s, 3H), -0.05 (s, 3H), -0.15 (s, 3H). 13 C NMR (101 MHz, CDCl3)δ 143.1, 132.6, 128.2, 127.1, 124.2, 123.1, 38.4, 27.2, 22.8, -3.4, -4.2, -4.9, -6.1. HRMS (ESI) (m / z): Calcd for C 15 H 24 Si2 [M+H] + : 261.1495, found:261.1491. This proves that the colorless oily liquid obtained in the above reaction is (S) -1,1,2,2,5-pentamethyl-3-phenyl-1,2,3,6-tetrahydro-1,2-disilazine.

[0108] Example 20: Preparation of (S)-1,1,2,2-tetramethyl-3-(4-(trifluoromethyl)phenyl)-1,2,3,6-tetrahydro-1,2-disilazine

[0109]

[0110] 1t and 2 were used as starting substrates to prepare the target product 3t, and the preparation method was the same as that in Example 1. The product was a white solid with a yield of 48% and an enantiomeric excess of 50%.

[0111] By hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 The colorless oily liquid product was analyzed by chemical shift and fragmentation analysis using C NMR, and its molecular weight was determined by high resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.1 Hz, 2H), 7.13 (d, J = 8.1 Hz, 2H), 5.85-5.80 (m,1H), 5.78- 5.71 (m, 1H), 3.01 (dt, J = 4.9, 2.1 Hz, 1H), 1.71 (dd, J = 13.7,8.7 Hz, 1H), 1.43- 1.35 (m, 1H), 0.21 (s, 3H), 0.11 (s, 3H), -0.02 (s, 3H), -0.14 (s, 3H). 13 C NMR (101 MHz, CDCl3)δ 147.2, 129.2, 127.0, 126.5 (q, J =32.0 Hz), 125.2 (q, J = 3.7 Hz), 124.8 (q, J = 272.7 Hz), 38.7, 17.3, -3.4, -3.6, -4.9, -6.2. 19 F NMR (376 MHz, CDCl3) δ -62.0. HRMS (ESI) (m / z): Calcd forC 15 H 21 F3Si2 [M+H] + : 315.1212, found: 315.1234. This proves that the white solid obtained in the above reaction is (S)-1,1,2,2-tetramethyl-3-(4-(trifluoromethyl)phenyl)-1,2,3,6-tetrahydro-1,2-disilazine.

[0112] The above description is only a general embodiment of the present invention and does not limit the present invention in any form. Any simple modification or equivalent change made to the above embodiment according to the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method for preparing a six-membered cyclic chiral disilic compound, characterized in that The steps include: Under nitrogen protection, 1,3-conjugated diene and dichlorobissilane are used as raw materials, and a cyclization reaction is carried out in a solvent system in the presence of a nickel catalyst, a Lewis acid, a ligand and a reducing agent; after the reaction is completed and cooled to room temperature, ethyl acetate is added to dilute, and extracted with a saturated sodium potassium tartrate solution and ethyl acetate, and the organic phase is dried and subjected to column chromatography to obtain the target product; The reaction route is as follows: ； Wherein the substituents R and R 1 , R 2 are each independently selected from alkyl, substituted alkyl, aryl, substituted aryl or hydrogen.

2. The preparation method according to claim 1, characterized in that: The nickel catalyst is nickel (II) trifluoromethanesulfonate.

3. The preparation method according to claim 1, characterized in that: The Lewis acid is trimethylaluminum.

4. The preparation method according to claim 1, characterized in that: The reducing agent is manganese powder.

5. The preparation method according to claim 1, characterized in that: The ligand is a composition of a chiral bidentate organophosphorus ligand (ligand 1) and a non-chiral bidentate nitrogen ligand (ligand 2); the ligand 1 is (R)-(-)-1-[(S)-2-diphenylphosphoferrocene]ethyl-di-tert-butylphosphine, and the ligand 2 is 2,2'-bipyridine.

6. The preparation method according to claim 1, characterized in that: The solvent is a mixture of 1,3-dimethyl-2-imidazolidinone and n-hexane, and the volume ratio of the two is 1:20 to 1:

2.

7. The preparation method according to claim 1, characterized in that: During the reaction, the molar ratio of 1,3-conjugated diene to dichlorodisilane is 1:

2.

8. The preparation method according to claim 1, 2, 3 or 4, characterized in that: The molar ratio of 1,3-conjugated diene to nickel catalyst is controlled to be 1:0.05~1:0.20; The molar ratio of 1,3-conjugated diene to Lewis acid is controlled to be 1:0.5~1:4; The molar ratio of 1,3-conjugated diene to reducing agent is controlled to be 1:0.5~1:

4.

9. The preparation method according to claim 1 or 5, characterized in that: The molar ratio of 1,3-conjugated diene to ligand 1 is controlled to be 1:0.05-1:0.20, and the molar ratio of 1,3-conjugated diene to ligand 2 is controlled to be 1:0.05-1:0.

20.

10. The preparation method according to claim 1, characterized in that: The cyclization reaction temperature is 30-70°C and the reaction time is 4-15 h.

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