A beta-alkyl substituted silane compound, a preparation method and application thereof

Abstract

This invention relates to the field of organic synthesis, specifically to a β-alkyl-substituted silane compound, its preparation method, and its applications. The silane compound is a cyclosilane compound or a linear silane compound. The molecular formula of the cyclosilane compound is: [Insert molecular formula here], and the molecular formula of the linear silane compound is: R [Insert molecular formula here] 1 -R 7 It is any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester, cyano, nitro, sulfonyl, heteroatom, and hydrogen atom; R 8 -R 10 The silane compound is any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester, cyano, nitro, sulfonyl, heteroatom, and hydrogen atom; n is any integer from 1 to 7. The silane compounds of this invention are a novel class of compounds that can be used to prepare silicon-containing polymers or derivatives of cyclic silane bioactive molecules. They achieve free radical addition reactions of unsaturated hydrocarbons or unsaturated amines with silanes, and the preparation method is simple and efficient.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, specifically to a β-alkyl-substituted silane compound, its preparation method, and its applications. Background Technology

[0002] β-alkyl-substituted cyclosilanes and linear silanes represent a novel class of compounds. We provide a mild and green photocatalytic synthesis method for this class of compounds, with broad substrate adaptability. To our knowledge, prior to this method, no other means existed for synthesizing these compounds. Silicon belongs to the same group as carbon, and its physicochemical properties are similar to those of carbon. However, studies have shown that using silicon atoms instead of carbon atoms in pharmaceuticals exhibits better effects, such as greater cell penetration, higher bioactivity, and lower toxicity. [a) Daud, A.;Valkov, N.;Centeno, B.;Derderian, J.;Sullivan, P.;Munster, P.;Urbas, P.;DeConti, RC;Berghorn, E.;Liu, Z.;Hausheer, F.;Sullivan, D.Phase II Trial of Karenitecin in Patients with Malignant Melanoma:Clinical and Translational Study.Clin.

[0003] Cancer Res.2005,11,3009-3016.b) Liu, B.; Gai, K.; Qin, H.; Wang, J.; Liu, X.; Cao, Y.; Lu, Q.; Lu, D.; Chen, D.; Shen, H.; Song, W.; Mei, J.; Wang, X.; Xu, H.; Zhang, Y. Discovery of a Silicon-Containing Pan-Genotype Hepatitis C Virus NS5A Inhibitor. J. Med. Chem. 2020, 63, 5312-5323. c) Tacke, R.; Popp, F.; Müller, B.; Theis, B.; Burschka, C.; Hamacher, A.; Kassack, MU; Schepmann, D.; Wünsch, B.; Jurva, U.; Wellner, E. Sila-Haloperidol, a Silicon Analogue of the Dopamine (D2) Receptor Antagonist Haloperidol: Synthesis, Pharmacological Properties, and Metabolic Fate. Chem Med Chem 2008, 3, 152-164.]. Currently, the realization of silicon atom β-substituent functionalization reactions mainly focuses on a small number of Kassin insertion reactions. [a) ZJ Garlets, E.F. Hicks, J. Fu, E.A. Voight and H. M. M. Davies, Org. Lett., 2019, 21, 4910. b) ZJ Garlets and H. M. M. Davies, Org. Lett., 2018, 20, 2168.] However, this type of reaction suffers from drawbacks such as poor substrate adaptability, harsh reaction conditions, and the use of precious metals. Therefore, it is necessary and promising to develop a new strategy that allows the reaction to be carried out under mild and environmentally friendly conditions while addressing the limitations of substrate availability. Summary of the Invention

[0004] One of the objectives of this invention is to provide a β-alkyl-substituted silane compound, which is a novel type of compound that can be used to prepare silicon-containing polymer materials or derivatives with cyclic silane bioactive molecules.

[0005] The second objective of this invention is to provide a method for preparing β-alkyl-substituted silane compounds, which has good substrate versatility and functional group tolerance, and is simple, efficient, green, and environmentally friendly.

[0006] A third objective of this invention is to provide an application of a β-alkyl-substituted silane compound.

[0007] One of the solutions adopted to achieve the objective of this invention is: a β-alkyl-substituted silane compound, wherein the silane compound is a cyclosilane compound or a straight-chain silane compound, and the molecular formula of the cyclosilane compound is:

[0008] The molecular formula of the straight-chain silane compound is:

[0009] Among them, R 1 -R 7 It can be any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester, cyano, nitro, sulfonyl, heteroatom, and hydrogen atom, and can be the same or different; R 8 R 9 R 10 It can be any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester, cyano, nitro, sulfonyl, heteroatom, and hydrogen atom, and can be the same or different; n is any integer from 1 to 7.

[0010] Preferably, the alkyl group has 1-20 carbon atoms and is a straight-chain, cyclic, or branched structure; the alkyl group has one or more substituents, and when it has multiple substituents, the substituents can be the same or different, and their positions can be the same or different.

[0011] Preferably, the aryl group has one or more substituents; when multiple substituents are present, the substituents may be the same or different.

[0012] The second objective of this invention is achieved by a method for preparing the β-alkyl-substituted silane compound, which involves mixing an unsaturated hydrocarbon or unsaturated hydrocarbon amine, silane, a photocatalyst, and an organic solvent, stirring and reacting the mixture under light and at temperatures ranging from -78°C to 180°C, followed by separation and purification to obtain the β-alkyl-substituted silane compound.

[0013] The reaction temperature ranges from -78°C to 180°C. The reaction time is between 3 and 24 hours. After the reaction is complete, the reaction product undergoes post-processing, including purification methods such as filtration, concentration, recrystallization, and column chromatography.

[0014] The filtration process can be performed using a sand core funnel under reduced pressure.

[0015] The concentration process can be carried out by methods such as atmospheric distillation, vacuum distillation, or vacuum concentration using a rotary evaporator.

[0016] The purification process involves obtaining a pure product through column chromatography.

[0017] The reaction formula of the method of the present invention can be expressed as follows:

[0018]

[0019] In this context, compound A represents unsaturated hydrocarbons or amines, compound B represents various silanes, and compound G represents β-alkyl-substituted cyclosilanes and straight-chain silanes.

[0020] Preferably,

[0021] The molecular structural formula of the unsaturated hydrocarbon is as follows:

[0022] The molecular structural formula of the unsaturated amine is as follows:

[0023] The molecular structural formula of the silane is:

[0024] Preferably, the photocatalyst is tris[2-phenylpyridine-C2,N]iridium(III), bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate), bis[2-(2,4-difluorophenyl)-5-methylpyridine][2,2'-bi(tetra-tert-butylpyridine)]iridium di(hexafluorophosphate), bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bipyridine]iridium di(hexafluorophosphate), [2,2'-bi(4-tert-butylpyridine)]bis[2-(2,4-difluorophenyl)pyridine]iridium(III) hexafluorophosphate, (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2 (-pyridyl)phenyl]iridium(III) hexafluorophosphate, bis(2-methyl-3-phenylpyrazine-C2,N)iridium acetylacetonate, bis(2,3-diphenylpyrazine-C2,N)iridium acetylacetonate, bis(2,3-diphenylquinoxaline)iridium acetylacetonate, bis(2-phenylpyrimidine-C2,N)iridium acetylacetonate, (2,2'-bipyridine)bis[2-(4-fluorophenyl)pyridine]iridium(III) hexafluorophosphate, (2,2'-bipyridine)bis[2-(2,4-difluorophenyl)pyridine]iridium(III) hexafluorophosphate, (2,2'-bipyridine)bis[2-(4-tert-butylphenyl)pyridine]iridium(III) hexafluorophosphate, (2-2'-bi(4-tert-butyl ...phenyl)pyridine]bis[2-(4-tert-butylpyridine)bis[2-(4-tert-butylphenyl)pyridine]bis[2-(4-tert-butylphenyl)pyridine]bis[2-(4-tert-butylphenyl)pyridine]bis[2-(4-tert-butylphenyl)pyridine]bis[2-(4-tert-butylphenyl [2-(4-tert-butylphenyl)pyridine]iridium(III) hexafluorophosphate, (1,10-phenanthroline)bis[2-(4-tert-butylphenyl)pyridine]iridium(III) hexafluorophosphate, tris(2-(4-fluorophenyl)pyridine)iridium, tris[2-(4,6-difluorophenyl)pyridine-C2,N]iridium(III), bis[2-(3-tert-butylphenyl)-4-tert-butylpyridine][2,2'-bi(4-tert-butylpyridine)]iridium(III) hexafluorophosphate, dichlorotetra(2-(2-pyridyl)phenyl)diiridium(III), tris(2-(4-trifluoromethylphenyl)pyridine)iridium, [2,2'-bi(4-tert-butylpyridine)]bis[2-(4-fluorophenyl)pyridine]iridium(III) hexafluorophosphate Fluorophosphates, Rhodamine 6G, Tris(1,10-phenanthroline)ruthenium(II)bis(hexafluorophosphate), Tris(4,4'-dimethyl-2,2'-bipyridine)ruthenium(III)(hexafluorophosphate), Tris(2,2'-bipyrazine)ruthenium di(hexafluorophosphonic acid), Tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate), Tris(2,2'-bipyridine) Ruthenium di(perchloric acid) salt, tris(2,2'-bipyridine)ruthenium di(tetrafluoroborate) salt, tris(2,2'-bipyridine)ruthenium(II) chloride hexahydrate, 9-trimethyl-10-phenylacridin-10-tetrafluoroborate, 2,3,5,6-tetra(9-carbazolyl)-terephthalonitrile, tetrabutylammonium decatungstate, anthraquinone, benzophenone, 2,4,5,Any one of the following: 6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN), derivatives of 4CzIPN, tris(2,2'-bipyridine)ruthenium(II) chloride hexahydrate, and Solvent Red 43.

[0025] Preferably, the organic solvent is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dimethyl ethylenediether, methyl tert-butyl ether, 1,4-epoxyhexanes, 1,3-epoxyhexanes, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 Saturated alkanes, C 3-12 Fluorinated or chlorinated alkanes, benzene, toluene, xylene, trimethylbenzene, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, N-methylpyrrolidone, acetonitrile, C 3-12 At least one of saturated alkyl nitriles.

[0026] Preferably, the molar ratio between the unsaturated hydrocarbon or unsaturated amine and silane is 1:1-10; the amount of catalyst used is 0.15% to 10% of the molar amount of the unsaturated hydrocarbon or unsaturated amine; and the concentration of the unsaturated hydrocarbon or unsaturated amine in the mixed solution is between 0.1M and 1M.

[0027] Preferably, the wavelength of the illumination is between 365-750nm, and the power of the light source is between 1W-60W.

[0028] The solution adopted to achieve the third objective of this invention is: the application of the β-alkyl-substituted silane compound, wherein the silane compound is used to prepare silicon-containing polymer materials or to prepare derivatives with cyclic silane bioactive molecules.

[0029] The present invention has the following advantages and beneficial effects:

[0030] (1) The β-alkyl-substituted silane compounds of the present invention are a new type of compound that can be used to prepare high molecular weight silicon-containing materials or to prepare derivatives of cyclic silicon bioactive molecules.

[0031] (2) The preparation method of the present invention realizes the free radical addition reaction of unsaturated hydrocarbons or unsaturated amines and silanes, which is a new reaction mode and provides a simple and efficient method for synthesizing β-alkyl substituted cyclosilanes and straight-chain silanes.

[0032] (3) The preparation method of the present invention is carried out under redox neutral conditions, and the reaction conditions are simple, efficient and mild.

[0033] (4) The reaction conditions involved in the preparation method of the present invention have good functional group tolerance and substrate universality, and can be compatible with various functional groups such as ester group, halogen, carbonyl group, etc. Various straight-chain or branched alkyl groups can also complete the reaction.

[0034] (5) The preparation method of the present invention can perform post-modification of complex bioactive molecules and drug molecules. Detailed Implementation

[0035] To better understand the present invention, the following embodiments are further illustrations of the present invention, but the content of the present invention is not limited to the following embodiments.

[0036] Example 1:

[0037]

[0038] In a glove box, TBADT (tetrabutylamine decapolytungstate, 33.2 mg, 5.0 mmol%), dried MeCN (acetonitrile, 1 mL), A (54.6 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 390 nm LED lamp of 6 W. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G1 (83.5 mg white solid, 84% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.57(d,J=6.4Hz,2H),7.49(d,J=8.7Hz,2H),7.46–7.35(m,8H),7.07(d,J=7.9Hz,2H),6.91(s,4H),5.04(d, J=6.5Hz,1H),4.11–4.03(m,1H),2.60–2.46(m,1H),2.34(s,3H),2.26(s,3H),1.69–1.61(m,1H),1.26–1.20(m,1H),1.20–1.08(m,2H). 13C NMR (151MHz, CDCl3, 25℃) δ142.9,137.6,136.9,136.5,135.6,134.8,134.6,134.2,130.1,13 0.0,129.2,128.8,128.2,128.1,127.3,127.2,66.1,38.2,21.6,21.2,17.7,17.6.HRMS(ESI - ,m / z):calcd for C 30 H 32 NO2SSi + (M+H) + :498.1918;Found:498.1916。

[0039] Example 2:

[0040]

[0041] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried DMF (N,N-dimethylformamide, 1 mL), A (58.6 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G2 (82.9 mg white solid, 80% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.56(d,J=6.4Hz,2H),7.48(d,J=8.3Hz,2H),7.46–7.36(m,8H),7.10–7.05(m,4H),6.96(d,J=8 .4Hz,2H),5.25(d,J=6.3Hz,1H),4.12–4.07(m,1H),2.56–2.43(m,1H),2.36(s,3H),1.70–1.62(m,1H),1.23–1.05(m,3H). 13C NMR (151MHz, CDCl3, 25℃) δ143.3,138.1,137.4,135.3,134.8,134.6,133.9,133.1,130.2(2C),129.4,128.8,128.3(2C),128.2,127.3 65.8,38.1,21.6,17.7,17.6.HRMS(ESI - ,m / z):calcd for C 29 H 29 ClNO2SSi + (M+H) + :518.1371;Found:518.1368.

[0042] Example 3:

[0043]

[0044] In a glove box, FeCl3 (ferric chloride, 1.6 mg, 5.0 mmol%), dried MeCN (1 mL), A (63.4 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 12 W 390 nm LED lamp. The reaction mixture was stirred at 80 °C for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (6 / 1–4 / 1, v / v) to give the target compound G3 (73.6 mg white solid, 68% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.79 (d, J=8.3Hz, 2H), 7.55 (d, J=6.3Hz, 2H), 7.4 8(d,J=8.3Hz,2H),7.46–7.41(m,4H),7.40–7.35(m,4H),7.10(d,J=8.3Hz,2 H),7.06(d,J=8.0Hz,2H),5.16(d,J=6.3Hz,1H),4.20–4.14(m,1H),3.90(s ,3H),2.58–2.45(m,1H),2.32(s,3H),1.70–1.63(m,1H),1.24–1.11(m,3H). 13C NMR (151MHz, CDCl3, 25℃) δ166.9,144.8,143.3,137.3,135.2,134.8,134.6,133.8,130.3,130.2 ,129.5,129.4,129.1,128.3,128.2,127.4,127.2,66.0,52.2,38.1,21.5,17.8,17.7.HRMS(ESI - ,m / z):calcdfor C 31 H 32 NO4SSi + (M+H) + :542.1816; Found:542.1814.

[0045] Example 4:

[0046]

[0047] In a glove box, CuCl2 (copper chloride, 33.2 mg, 5.0 mmol%), dried DMSO (dimethyl sulfoxide, 1 mL), A (55.4 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 30 W 390 nm LED lamp. The reaction mixture was stirred at 120 °C for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G4 (73.1 mg white solid, 73% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.57(d,J=6.5Hz,2H),7.50(d,J=8.3Hz,2H),7.47–7.40(m,4H),7.38(t,J=7.8Hz,4H),7.09(d,J=8.0Hz,2H),7.02–6. 97(m,2H),6.80(t,J=8.6Hz,2H),5.35(d,J=6.4Hz,1H),4.14–4.08(m,1H ),2.56–2.47(m,1H),2.35(s,3H),1.70–1.64(m,1H),1.27–1.08(m,3H). 13C NMR (151MHz, CDCl3, 25℃) δ162.0(d,J=245.4Hz),143.1,137.5,135.4,135.3(d,J=3.2Hz),134.8,134.6,134.0,1 30.2(d,J=13.6Hz),129.3,129.0,128.9,128.2,128.1,127.2,115.0(d,J=21.6Hz),65.7,38.2,21.6,17.7,17.6. 19 F NMR (376MHz, CDCl3, 25℃) δ-115.4.HRMS (ESI - ,m / z):calcd for C 29 H 29 FNO2SSi + (M+H) + :502.1667; Found:502.1664.

[0048] Example 5:

[0049]

[0050] In a glove box, BP (benzophenone, 1.8 mg, 5.0 mmol%), dried MeCN (1 mL), A (56.8 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 360 nm LED lamp (60 W). The reaction mixture was stirred at -80 °C for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G5 (60.9 mg white solid, 60% yield). 1 H NMR (400MHz, CDCl3, 25℃) δδ7.56–7.50(m,4H),7.46–7.36(m,10H),7.18(d,J=7.9Hz,2H),7.11(d,J=8.0Hz,2H), 5.51(d,J=6.0Hz,1H),4.18–4.12(m,1H),2.55–2.42(m,1H),2.37(s,3H),1.68–1.63(m,1H),1.23–1.08(m,3H). 13C NMR (151MHz, CDCl3, 25℃) δ145.3,143.6,137.1,135.0,134.8,134.5,133.5,132.0,130.4,1 30.3,129.5,128.3,128.2(2C),127.2,118.8,111.0,65.9,38.0,21.6,17.8,17.7.HRMS(ESI - ,m / z):calcd forC 30 H 28 N2O2SSi + (M+H) + :509.1714;Found:509.1712。

[0051] Example 6:

[0052]

[0053] In a glove box, AQ (anthraquinone, 33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (49.8 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 1 W 420 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G6 (69.1 mg yellow solid, 73% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.63–7.57(m,4H),7.49–7.37(m,8H),7.15(d,J=8.0Hz,2H),7.11(d,J=1.8Hz,1H),6.12–6.08(m,1H),5.92 (d,J=3.2Hz,1H),5.01(d,J=8.7Hz,1H),4.31(t,J=8.4Hz,1H),2.79–2.67(m,1H),2.36(s,3H),1.68–1.62(m,1H),1.35–1.21(m,3H). 13C NMR (151MHz, CDCl3, 25℃) δ152.0,143.0,141.8,137.7,135.6,134.9,134.6,134.3,130. 1(2C),129.4,128.2,128.1,127.1,110.0,107.9,59.0,36.2,21.6,17.5,17.1.HRMS(ESI - ,m / z):calcd for C 27 H 28 NO3SSi + (M+H) + :474.1554;Found:474.1552。

[0054] Example 7:

[0055]

[0056] 1. In a glove box, 4-CzIPN (2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, 3.2 mg, 2.0 mmol%), dried Acetone (acetone, 1 mL), A (57.4 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 460 nm LED lamp (6 W). The reaction mixture was stirred at 40 °C for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G7 (71.5 mg white solid, 70% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.79(d,J=7.9Hz,2H),7.59(d,J=7.0Hz,2H),7.46–7.35(m, 8H),7.29–7.22(m,4H),7.16(t,J=7.3Hz,1H),7.03(d,J=7.4Hz,2H),4.54(d,J=8.1Hz ,1H),3.33–3.23(m,1H),2.57–2.47(m,2H),2.41(s,3H),2.40–2.32(m,1H),1.91–1.8 0(m,1H),1.69–1.60(m,1H),1.46–1.34(m,2H),1.25–1.17(m,1H),1.02–0.92(m,1H). 13C NMR (151MHz, CDCl3, 25℃) δ143.3,141.9,138.6,135.6,134.9,134.6,134.2,130.1(2C),129.8 ,128.5,128.4,128.2,128.1,127.2,126.0,61.3,35.8,34.3,31.4,21.7,17.2,16.5.HRMS(ESI - ,m / z):calcd for C 31 H 33 NO2SSi + (M+H) + :512.2074;Found:512.2070.

[0057] Example 8:

[0058]

[0059] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried PhCF3 (1 mL), A (44.6 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 390 nm LED lamp (60 W). The reaction mixture was stirred at -40 °C for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G8 (59.0 mg white solid, 66% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.78 (d, J=7.9Hz, 2H), 7.62 (d, J=5.9Hz, 2H), 7.4 9–7.35(m,8H),7.28–7.24(m,2H),4.71(d,J=7.8Hz,1H),2.70(q,J=7.7Hz,1 H),2.55–2.44(m,1H),2.41(s,3H),1.49–1.31(m,3H),1.23–1.14(m,1H),0 .84–0.74(m,1H),0.53–0.44(m,1H),0.33–0.20(m,2H),0.00–-0.08(m,1H). 13C NMR (151MHz, CDCl3, 25℃) δ143.1,139.0,135.9,134.9,134.6,134.4,130.0,129.9, 129.6,128.2,128.1,127.2,64.9,37.5,21.7,17.1,16.4,14.4,4.7,2.2.HRMS(ESI - ,m / z):calcd for C 26 H 30 NO2SSi + (M+H) + :448.1761;Found:448.1756.

[0060] Example 9:

[0061]

[0062] In a glove box, Eosin Y (Solvogen Red 43, 6.5 mg, 5.0 mmol%), dried DCM (dichloromethane, 1 mL), A (28.8 mg, 0.2 mmol), and B (89.6 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 550 nm LED lamp (24 W). The reaction mixture was stirred at 0 °C for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G9 (colorless oil, 52.3 mg, 71% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.69–7.64(m,2H),7.57–7.52(m,2H),7.48–7.37(m,6H),3.72(s,3H),3.68(s,3H),2.87–2.79(m,1H),2. 77–2.68(m,1H),2.63–2.56(m,1H),2.55–2.44(m,1H),1.70–1.64(m,1H),1.61–1.53(m,1H),1.48–1.39(m,1H),1.28–1.19(m,1H). 13C NMR (151MHz, CDCl3, 25℃) δ174.8,172.8,135.7,134.9,134.6,134.1,130.2,130.1,128.2,128.1,51.9,51.8,51.2,34.9,34.7,19.3,18.5.HRMS (ESI - ,m / z):calcd for C 21 H 25 O4Si + (M+H) + :369.1517;Found:369.1506.

[0063] Example 10:

[0064]

[0065] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried CHCl3 (chloroform, 1 mL), A (10.6 mg, 0.2 mmol), and B (179.6 mg, 0.8 mmol, 4.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–6 / 1, v / v) to give the target compound G10 (colorless oil, 23.3 mg, 42% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.69–7.65(m,2H),7.58–7.55(m,2H),7.47–7.39(m,6H),2.54–2 .47(m,1H),2.36(t,J=7.2Hz,2H),1.89–1.85(m,2H),1.76–1.72(m,2H),1.17–1.12(m,2H). 13 C NMR (151MHz, CDCl3, 25℃) δ136.1,134.8,134.6,134.5,130.1,130.0,128.3,128.2,120.0,36.8,31.9,20.0,15.5.HRMS(ESI - ,m / z):calcd forC 18 H 20 NSi + (M+H) +:278.1360; Found:278.1370.

[0066] Example 11:

[0067]

[0068] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried Et₂O (diethyl ether, 1 mL), A (40.8 mg, 0.2 mmol), and B (89.8 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G11 (colorless oil, 53.1 mg, 62% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ8.01(d,J=8.6Hz,2H),7.62(d,J=8.0Hz,2H),7.58(d,J=7.5Hz,1H),7.55(d,J=7.9Hz,2H),7.48(d,J=8.2Hz,2H),7.46–7. 37(m,6H),4.43–4.38(m,1H),4.17–4.13(m,2H),2.48–2.40(m,1H),2.28– 2.20(m,2H),1.76–1.63(m,2H),1.23–1.18(m,2H),1.16(d,J=7.2Hz,3H). 13 C NMR (151MHz, CDCl3, 25℃) δ195.5,170.2,136.4,136.4,134.9,134.8,134.6,133.6,130. 0,129.9,128.9,128.7,128.2,128.1,61.5,52.8,40.7,31.1,20.5,20.4,14.1.HRMS(ESI - ,m / z):calcd forC 27 H 29 O3Si + (M+H) + Found: 429.1881; Found: 429.1870.

[0069] Example 12:

[0070]

[0071] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (37.2 mg, 0.2 mmol), and B (89.8 mg, 0.4 mmol, 2.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G12 (colorless oil, 63.9 mg, 78% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.66(d,J=7.1Hz,2H),7.55(d,J=7.5Hz,2H),7.46–7.37(m,6H),4.23–4.15(m,4H),3.58(d,J=5.5Hz ,1H),2.38–2.28(m,1H),2.26–2.18(m,1H),1.64–1.57(m,2H),1.27(t,J=6.7Hz,6H),1.23–1.15(m,2H),1.08(d,J=6.7Hz,3H). 13 C NMR (151MHz, CDCl3, 25℃) δ169.8,168.9,136.3,135.0,134.7,134.6,130.0,129.9,12 8.2,128.1(3C),61.3,61.0,54.5,43.5,36.6,18.9,18.5,14.3,14.2,13.6.HRMS(ESI - ,m / z):calcd for C 24 H 31 O4Si + (M+H) + Found: 411.1986; Found: 411.1975.

[0072] Example 13:

[0073]

[0074] In a glove box, TBADT (3.3 mg, 1.0 mmol%), dried MeCN (1 mL), A (10.5 mg, 0.1 mmol), and B (224.4 mg, 1.0 mmol, 10.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 390 nm LED lamp of 6 W. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G13 (colorless oil, 22.7 mg, 69% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ8.54(d,J=6.2Hz,1H),7.68(d,J=7.8Hz,2H),7.60–7.56(m,3H),7.45–7.38(m,6H),7.15(d,J=7. 7Hz,1H),7.11–7.07(m,1H),2.85–2.82(m,2H),2.47–2.41(m,1H),1.99–1.95(m,2H),1.75–1.70(m,2H),1.25–1.20(m,2H). 13 C NMR (151MHz, CDCl3, 25℃) δ162.5,149.3,136.9,136.3,135.6,134.9,134.6,129.8(2C),128.1(2C),122.8,120.9,42.1,36.6,32.7,20.4.HRMS(ESI - ,m / z):calcd forC 22 H 24 NSi + (M+H) + :330.1673; Found:330.1663.

[0075] Example 14:

[0076]

[0077] In a glove box, AP (acetophenone, 0.045 mg, 0.15 mmol%), dried MeCN (1 mL), A (18.1 mg, 0.1 mmol), and B (224.4 mg, 1.0 mmol, 10.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G14 (colorless oil, 30.8 mg, 76% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ8.48(d,J=6.1Hz,2H),7.59–7.52(m,4H),7.43–7.36(m,6H),7.31–7.27(m,2H),7.24–7 .20(m,3H),7.17(d,J=6.1Hz,2H),4.01(t,J=7.3Hz,1H),2.30–2.23(m,3H),1.70–1.63(m,2H),1.23–1.17(m,2H). 13 C NMR (151MHz, CDCl3, 25℃) δ154.2,150.0,143.4,136.7,135.1,134.8,134.6,129.9(2 C),128.8,128.2,128.1,128.0,126.8,123.4,48.7,47.3,30.5,20.3,20.3.HRMS(ESI - ,m / z):calcd for C 28 H 28 NSi + (M+H) + Found: 406.1986; Found: 406.1974.

[0078] Example 15:

[0079]

[0080] In a glove box, TBADT (3.3 mg, 1.0 mmol%), dried MeCN (1 mL), A (14.7 mg, 0.1 mmol), and B (224.4 mg, 1.0 mmol, 10.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G15 (colorless oil, 28.2 mg, 76% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ9.07 (d, J = 3.0Hz, 1H), 8.15–8.12 (m, 1H), 7.68–7.64 (m, 2H), 7.58–7.55 (m, 2H), 7.45–7.37 (m, 6H), 7 .27–7.25(m,1H),2.90–2.87(m,2H),2.61(s,3H),2.44–2.38(m,1H),1.99–1.94(m,2H),1.72–1.69(m,2H),1.22–1.17(m,2H). 13 C NMR (151MHz, CDCl3, 25℃) δ196.8,167.5,149.9,136.8,135.9,135.4,134.9,134.6 ,130.2,129.9,129.8,128.2,128.1,122.9,41.8,36.9,32.7,26.8,20.4.HRMS(ESI - ,m / z):calcd for C 24 H 26 ONSi + (M+H) + :372.1778; Found:372.1767.

[0081] Example 16:

[0082]

[0083] In a glove box, TBADT (3.3 mg, 1.0 mmol%), dried MeCN (1 mL), A (17.7 mg, 0.1 mmol), and B (224.4 mg, 1.0 mmol, 10.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G16 (colorless oil, 23.3 mg, 58% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ9.13(d,J=2.1Hz,1H),8.19–8.17(m,1H),7.67–7.65(m,2H),7.57–7.55(m,2H),7.44–7.37(m,6H),7.22(d,J=8.1Hz,1H) ,4.39(t,J=7.1Hz,2H),2.90–2.87(m,2H),2.44–2.38(m,1H),1.97(d,J= 15.6Hz,2H),1.71–1.68(m,2H),1.40(t,J=7.1Hz,3H),1.22–1.17(m,2H). 13 C NMR (151MHz, CDCl3, 25℃) δ167.1,165.7,150.7,137.4,136.8,135.5,134.9,134.6,12 9.9,129.8,128.2,128.1,123.9,122.4,61.3,41.8,36.8,32.7,20.4,14.4.HRMS(ESI - ,m / z):calcd for C 25 H 28 O2NSi + (M+H) + Found: 402.1884; Found: 402.1875.

[0084] Example 17:

[0085]

[0086] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (117.2 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G17 (90.5 mg white solid, 82% yield). 1 H NMR (400MHz, CDCl3, 25℃) δ7.49–7.44(m,4H),7.35(d,J=8.2Hz,2H),7.33(s,4H),7.14–7.08(m,3H),7.03(d,J=8.0Hz,2H),7.00–6.96(m ,2H),5.31(d,J=7.3Hz,1H),4.16–4.11(m,1H),2.58–2.50(m,1H),2.32(s,3H),1.67–1.62(m,1H),1.32–1.28(m,1H),1.19–1.13(m,2H). 13 C NMR (151MHz, CDCl3, 25℃) δ43.0,139.3,137.6,136.8,136.7,136.2,135.9,133.4,132.1 ,129.3,128.6,128.5,128.3,127.4,127.2(2C),66.0,38.2,21.6,17.7,17.6.HRMS(ESI - ,m / z):calcd for C 29 H 28 Cl2NO2SSi + (M+H) + :552.0982; Found:552.0980.

[0087] Example 18:

[0088]

[0089] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (64.8 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G18 (colorless oil 70.7 mg, yield 84%, dr = 1:1). 1 H NMR (600MHz, CDCl3, 25℃) δ 1 H NMR(600MHz,Chloroform-d)δ7.56–7.50(m,3H,H+H'),7.50–7.45(m,1H,H+H'),7.44–7.29(m,3H,H+ H'),7.15–7.07(m,3H,H+H'),7.09–7.03(m,3H,H+H'),7.03–6.99(m,1H,H+H'),5.47–5.39(m,1H,H+ H'),4.14–4.07(m,1H,H+H'),2.55–2.46(m,1H,H+H'),2.33(s,3H,H+H'),1.51–1.46(m,1H,H),1.39 –1.32(m,1H,H'),1.07–0.92(m,2H,H+H'),0.90–0.84(m,1H,H+H'),0.50(s,3H,H),0.48(s,3H,H'). 13 C NMR (151MHz, CDCl3, 25℃) δ142.8(C+C'),139.7(C+C'),137.73(C+C'),137.4,1 36.9(C'),133.73,133.64(C'),129.9,129.7(C'),129.2(C+C'),128.1(C+C'), 128.0(C+C'),127.4,127.3(C'),127.2(C+C'),127.1(C+C'),66.3,66.2(C'), 38.7,37.9(C'),21.51,18.1,18.0(C'),17.9(C+C'),-0.2,-4.2(C').HRMS(ESI - ,m / z):calcd forC 24 H 28 NO2SSi+ (M+H) + :422.1605; Found:422.1595.

[0090] Example 19:

[0091]

[0092] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (100.8 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G19 (81.8 mg white solid, 80% yield, dr = 1:1). 1 H NMR (600MHz, CDCl3, 25℃) δ 1 H NMR(600MHz,Chloroform-d)δ7.55(d,J=8.3Hz,1H,H+H'),7.49(d,J=8.3Hz,1H,H+H'),7.46–7.41(m,2H,H+H'),7.39–7.34(m,2 H,H+H'),7.34–7.28(m,4H,H+H'),7.26–7.23(m,2H,H+H'),7.13–7.07(m,3H,H+H'),7.00(t,J=8.5Hz,2H,H+H'),6.96–6.88(m, 2H,H+H'),5.63(d,J=8.6Hz,1H,H),5.37(d,J=8.9Hz,1H,H'),4.22–4.08(m,1H,H+H'),2.28(s,3H,H+H'),2.15–2.05(m,1H,H+H '),1.88–1.81(m,1H,H+H'),1.54–1.48(m,1H,H+H'),1.42–1.19(m,4H,H+H'),0.88–0.79(m,1H,H+H'),0.64–0.54(m,1H,H+H'). 13C NMR (151MHz, CDCl3, 25℃) δ142.9,142.8(C'),139.8,139.7(C'),137.9,137.7(C'),137.1,137.0(C') ,134.7(C+C'),134.6,134.4(C'),134.3(C+C'),129.5,129.4(C'),129.3(C+C'),129.2(C+C'),128. 2(C+C'),128.1(C+C'),127.8(C+C'),127.3,127.2(C'),127.1(C+C'),127.00(C+C'),65.4(C+C'),4 2.5,42.4(C'),33.0,32.1(C'),23.4(C+C'),21.5(C+C'),15.1,13.6(C'),11.0,10.9(C').HRMS(ESI - ,m / z):calcd for C 31 H 34 NO2SSi + (M+H) + :512.2074; Found:512.2066.

[0093] Example 20:

[0094]

[0095] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (95.4 mg, 0.4 mmol, 2.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G20 (74.5 mg white solid, 75% yield, dr = 1:1). 1 H NMR (600MHz, CDCl3, 25℃) δ 11H NMR (600 MHz, Chloroform-d) δ 7.52–7.30 (m, 12H, H+H’), 7.13–7.06 (m, 3H, H+H’), 7.04–6.99 (m, 3H, H+H’), 6.98–6.89 (m, 1H, H+H’), 5.75–5.55 (m, 1H, H+H’), 4.20–4.13 (m, 1H, H+H’), 2.31 (s, 3H, H+H’), 2.20–2.07 (m, 1H, H+H’), 1.69–1.54 (m, 3H, H), 1.38–1.21 (m, 2H, H+H’), 1.05–0.89 (m, 3H, H’), 0.81–0.76 (m, 1H, H), 0.69–0.56 (m, 1H, H’). 13 13C NMR (151 MHz, CDCl3, 25 °C) δ 142.8 (C+C’), 140.6, 140.4 (C’), 137.8, 136.1 (C’), 134.8 (C+C’), 134.7 (2C, C+C’), 129.6 (C+C’), 129.5 (C+C’), 129.2 (C+C’), 128.2 (C+C’), 128.1 (C+C’), 128.0 (2C, C+C’), 127.2 (C+C’), 127.1 (C+C’), 127.0 (C+C’), 64.8, 64.0 (C’), 48.0, 47.5 (C’), 31.0, 30.9 (C’), 21.5 (C+C’), 16.3, 16.2 (C’), 11.5, 10.9 (C’). HRMS (ESI - , m / z): calcd for C 30 1H 32 NO2SSi + (M+H) + : 498.1918; Found: 498.1922.

[0096] Example 21:

[0097]

[0098] In a glove box, AQ (4.2 mg, 10.0 mmol%), dried MeCN (1 mL), A (47.2 mg, 0.2 mmol), and B (468.9 mg, 2.0 mmol, 10.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 420 nm LED lamp (6 W). The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G21 (60.2 mg of colorless oil, 64% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ 1 H NMR(600MHz,Chloroform-d)δ7.93(t,J=7.0Hz,4H),7.54(t,J=7.0Hz,2H),7.46–7.40(m,6H),7.29–7.24(m,3H),5.20(t,J=6.5 Hz,1H),2.12–2.07(m,1H),2.06–1.96(m,1H),1.77–1.70(m,1H),1.31–1.25(m,4H),0.97–0.88(m,11H),0.76(t,J=8.4Hz,4H). 13 C NMR (151MHz, CDCl3, 25℃) δ196.2,138.1,136.3,136.2,134.1,133.5,129.0(2C),1 28.8,128.7(2C),127.8,56.1,40.1,28.7,23.0,21.3,18.7,17.5,15.8.HRMS(ESI - ,m / z):calcd for C 31 H 39 O2Si + (M+H) + :471.2714; Found:471.2701.

[0099] Example 22:

[0100]

[0101] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (288.6 mg, 2.0 mmol, 10.0 equiv.) were added to a dry photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 420 nm LED lamp (6 W). The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (20 / 1–10 / 1, v / v) to give the target compound G22 (50.0 mg of colorless oil, 62% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ 1 H NMR(600MHz,Chloroform-d)δ7.56(d,J=8.3Hz,2H),7.17–7.12(m,3H),7.10(d,J=8.0Hz,2H),7.04–6.99(m,2H),5.27(d,J=7.6Hz,1H) ,4.20–4.15(m,1H),2.34(s,3H),1.70–1.61(m,2H),0.81(t,J=8.0Hz,9H),0.47–0.41(m,1H),0.39(q,J=7.9Hz,6H),0.21–0.15(m,1H). 13 C NMR (151MHz, CDCl3, 25℃) δ143.0,141.0,137.9,129.4,128.4,127.3,127.2,126.8,61.2,32.0,21.5,7.5,7.4,3.1.HRMS(ESI - ,m / z):calcd for C 22 H 34 NO2SSi + (M+H) + Found: 404.2074; Found: 404.2080.

[0102] Example 23:

[0103]

[0104] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (264.5 mg, 2.0 mmol, 10.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 420 nm LED lamp (6 W). The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–5 / 1, v / v) to give the target compound G23 (42.2 mg of colorless oil, 54% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ 1 H NMR(600MHz,Chloroform-d)δ7.54(d,J=8.3Hz,2H),7.18–7.13(m,3H),7.11(d,J=7.7Hz,2H),7.03–6.99(m,2H),5.12(d, J=7.4Hz,1H),4.25–4.21(m,1H),2.35(s,3H),1.86–1.72(m,3H),0.91–0.87(m,6H),0.57–0.50(m,5H),0.45–0.40(m,1H). 13 C NMR (151MHz, CDCl3, 25℃) δ143.1,141.0,137.8,129.4,128.5,127.4,127.2,126.7,60.6,31.3,21.6,10.3,6.7,6.6,6.2,6.1.HRMS(ESI - ,m / z):calcd for C 20 H 30 NO3SSi + (M+H) + :392.1710; Found:392.1705.

[0105] Example 24:

[0106]

[0107] In a glove box, TBADT (33.2 mg, 5.0 mmol%), dried MeCN (1 mL), A (51.8 mg, 0.2 mmol), and B (416.7 mg, 2.0 mmol, 10.0 equiv.) were added to a dried photoreaction tube equipped with a magnetic stirrer. The photoreaction tube was sealed, removed from the glove box, and irradiated with a 420 nm LED lamp (6 W). The reaction mixture was stirred at room temperature for 12 hours. The LED lamp was then turned off, and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200–300 mesh) and eluted with PE / EA (10 / 1–5 / 1, v / v) to give the target compound G24 (62.6 mg of colorless oil, 67% yield). 1 H NMR (600MHz, CDCl3, 25℃) δ 1 H NMR(600MHz,Chloroform-d)δ7.53(d,J=8.3Hz,2H),7.22–7.18(m,2H),7.17–7.13(m,3H),7.12–7.09(m,2H),6.99–6.94(m,3H),6.76–6.72 (m,2H),4.89(d,J=7.5Hz,1H),4.22–4.18(m,1H),2.34(s,3H),1.83–1.73(m,2H),0.91–0.87(m,6H),0.70–0.63(m,5H),0.48–0.42(m,1H). 13 C NMR (151MHz, CDCl3, 25℃) δ155.3,143.1,140.7,137.9,129.6,129.4,128.6, 127.5,127.2,126.7,121.6,120.0,60.7,31.0,21.6,9.5,6.6,5.4.HRMS(ESI - ,m / z):calcd for C 26 H 34 NO3SSi + (M+H) + :468.2023;Found:468.2030。

[0108] The above description is merely a preferred embodiment of the present invention, and should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A kind β A method for preparing alkyl-substituted silane compounds, characterized in that: Unsaturated hydrocarbons or unsaturated hydrocarbon amines, silanes, photocatalysts, and organic solvents are mixed and reacted under light irradiation and at temperatures ranging from -78°C to 180°C with stirring. The mixture is then separated and purified to obtain the desired product. β -alkyl-substituted silane compounds; The molecular structural formula of the silane is as follows: , , , , , , , At least one of them; The molecular structural formula of the unsaturated hydrocarbon or unsaturated hydrocarbon amine is as follows: , , , , , , , , , , , , , , , , , , At least one of them; The β The molecular structural formula of the alkyl-substituted silane compound is: , , , , , , , , , , , , , , , , , , , , , , At least one of them; The photocatalyst is any one of 2,3,5,6-tetra(9-carbazolyl)-terephthalonitrile, tetrabutylammonium decatungstate, anthraquinone, benzophenone, 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, and Solvent Red 43; The wavelength of the illumination is between 365 and 750 nm.

2. The method of claim 1, β Process for the preparation of alkyl-substituted silane compounds, characterized in that The organic solvent is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dimethyl ethylene glycol, methyl tert-butyl ether, 1,4-epoxyhexanes, 1,3-epoxyhexanes, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 Saturated alkanes, C 3-12 Fluorinated or chlorinated alkanes, benzene, toluene, xylene, trimethylbenzene, dimethyl sulfoxide, N , N -Dimethylformamide, N , N -Dimethylacetamide, acetone, N -Methylpyrrolidone, acetonitrile, C 3-12 At least one of saturated alkyl nitriles.

3. The method of claim 1, β Process for the preparation of alkyl-substituted silane compounds, characterized in that The molar ratio between the unsaturated hydrocarbon or unsaturated hydrocarbon amine and silane is 1:1-10; the amount of catalyst used is 0.15% to 10% of the molar amount of unsaturated hydrocarbon or unsaturated hydrocarbon amine, and the concentration of unsaturated hydrocarbon or unsaturated hydrocarbon amine in the mixed solution is between 0.1M and 1M.

4. The method according to claim 1 β A method for preparing alkyl-substituted silane compounds, characterized in that: The power of the light source is between 1 W and 60 W.

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