A photocatalytic synthesis method of a dialkyl sulfide compound

Abstract

The application belongs to the technical field of chemical synthesis and relates to a photocatalytic synthesis method of a dialkyl sulfide compound, which uses a phosphine catalyst as a photocatalyst, performs a sulfurization reaction on unsaturated hydrocarbon in a photocatalytic manner, and synthesizes the dialkyl sulfide compound. The method has mild conditions, good functional group compatibility, good applicability and biological compatibility, a wide substrate range, and simple operation, and is conducive to the industrial preparation of sulfide compounds.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis technology and relates to a photocatalytic synthesis method for dialkyl sulfide compounds. Background Technology

[0002] Thioethers are a wide range of organosulfur compounds. In medicine, thioethers are not only the main structures of many natural active molecules, but also important components of many drugs, exhibiting significant biological activities such as antitumor, anti-inflammatory, antibacterial, and antiviral activity (Top. Curr. Chem (Z). 2018, 376, 5; Curr. Top. Med. Chem. 2016, 16, 1200-1216; Curr. Drug Targets. 2022, 23, 170-219). In pesticides, some compounds containing thioether structures possess biological activity and are used as insecticides, fungicides, or herbicides (J. Heterocycl. Chem. 2021, 58, 1225-1251). Therefore, developing new synthetic methods for thioether compounds and constructing novel thioether structures are of significant research importance and promising application prospects for drug development.

[0003] Currently, there are many methods for synthesizing thioethers. The most common method is the nucleophilic substitution reaction of halogenated hydrocarbons with sodium sulfide to synthesize thioethers. This strategy is only suitable for simple halogenated hydrocarbons, or requires the preparation of complex halogenated hydrocarbons, and the reaction requires high temperature, highly polar solvents, and is difficult to separate and purify (CN105218418 A). In addition, Zeng et al. reported a method for synthesizing dibenzyl thioethers by nucleophilic substitution of quaternary ammonium salts with sodium sulfide. This method requires the preparation of highly reactive quaternary ammonium salts, has a limited substrate scope, and produces a single product type (Asian J. Org. Chem. 2021, 10, 1687-1690). Xiong et al. developed a method for synthesizing thioethers using the ionic liquid 1-alkyl-3-methylimidazolium carboxylate as a catalyst, utilizing the Michael addition reaction of H2S with α,β-unsaturated carboxylic acid esters. This method is only suitable for electron-deficient unsaturated alkenes, and has a large substrate scope limitation (Green Energy Environ. 2024, 9, 1440-1448).

[0004] In summary, existing methods for preparing thioether compounds using inexpensive and readily available sodium sulfide or hydrogen sulfide as sulfur sources have many problems, such as a large limitation on the substrate range. Summary of the Invention

[0005] To address the limitations of existing methods for preparing thioether compounds, such as the limited substrate scope, this invention aims to provide a photocatalytic synthesis method for dialkyl thioether compounds. This method utilizes organophosphorus photocatalysis to sulfide olefins, resulting in the synthesis of dialkyl thioether compounds. The method offers mild conditions, good functional group compatibility, excellent applicability and biocompatibility, a broad substrate scope, and simple operation, making it beneficial for the industrial preparation of thioether compounds.

[0006] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a photocatalytic synthesis method for dialkyl sulfide compounds, comprising: using unsaturated hydrocarbons and sulfur sources as raw materials, using a phosphine catalyst as a photocatalyst, and carrying out the reaction in a solvent and under inert gas protection, under blue light irradiation, to obtain dialkyl sulfide compounds.

[0007] Preferably, the unsaturated hydrocarbon is an olefin or an alkyne.

[0008] Furthermore, the olefin has the structural formula shown in formula (1) or formula (2), and the alkyne has the structural formula shown in formula (3):

[0009] R1, R2 and R3 are each independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, ester group, or R2 and R3 are connected to form a cycloalkyl or substituted cycloalkyl; R4 is selected from oxygen, alkyl, substituted alkyl, substituted amino group, phthalic acid group; R5 and R6 are each independently selected from hydrogen, alkyl, aryl, substituted aryl.

[0010] Furthermore, the olefin is 1-allyl-2-methoxybenzene, allyl phenyl carbonate, 1-allylbenzotriazole, vinyl benzoate, vinyl acetate, allyl ether, 9-bromo-1-nonene, 4-allyl anisole, styrene, diallyl phthalate, but-3-en-1-yl(4-chlorophenyl) sulfide, diethyl allyl malonate, diethyl diallyl malonate, 3-methylbut-3-enyl benzoate, 3-cyclohexanediol. Dimethyl pentene-1,1-dicarboxylate, N,N-diallylcarbamate tert-butyl ester, N,N-diallyl-4-methylbenzenesulfonamide, N,N-diallyl-3-bromo-4-chlorobenzenesulfonamide, allyl-tetra-O-acetyl-β-D-glucopyranoside, N-(4-phenylthiazol-2-yl)hept-6-enamide, 3-allyl-3-toluenesulfonylhex-5-en-2-one, pent-4-en-1-yl-4-( (1,1'-Biphenyl)-4-yl)-4-oxobutyrate, pent-4-en-1-yl 2-(4-(2-(4-chlorobenzoamido)ethyl)phenoxy)-2-methylpropionate, pent-4-en-1-yl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate, 3-(4-isobutylphenyl)propionate 3-methylbut-3-en-1-yl ester, 3-methylbut- One of the following: 3-en-1-yl 2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazolyl-5-carboxylic acid ester, (1r,4R)-N-((R)-1-(diallylamino)-1-oxo-3-phenylpropan-2-yl)-4-isopropylcyclohexane-1-carboxamide, and 4-chloro-N-(4-((1-(diallylamino)-2-methyl-1-oxopropan-2-yl)oxy)phenethyl)benzamide; The alkyne is 1-ethynyl-4-methylbenzene.

[0011] Preferably, the sulfur source is sodium sulfide, hydrogen sulfide, thiol, or dithiol; when the sulfur source is sodium sulfide or hydrogen sulfide, the method further includes using an organic acid as an additive.

[0012] Furthermore, the structural formula of the thiol is shown in formula (4), and the structural formula of the dithiol is shown in formula (5):

[0013] R7 is selected from alkyl, substituted alkyl, aryl, substituted aryl, and glycosyl; R8 is an alkyl group.

[0014] Furthermore, the thiol is benzyl thiol, 4-methylthiophenol, N-acetyl-L-cysteine ​​methyl ester, thiobenzoic acid, 1-thio-β-D-glucose tetraacetate, 1-thio-β-D-glucose tetraacetate, thioacetic acid, or pentafluoropentanethiol; the dithiol is 1,2-ethanedithiol or 1,2-propanedithiol.

[0015] Furthermore, when the sulfur source is sodium sulfide, the phosphine catalyst is 1,1'-binaphthyl-2,2'-bisdiphenylphosphine; when the sulfur source is hydrogen sulfide, thiol or dithiol, the phosphine catalyst is 1,1'-binaphthyl-2,2'-bisdiphenylphosphine or a phosphine salt as shown in formula (6);

[0016] Where X is Cl — or Br — .

[0017] Furthermore, the organic acid is formic acid, acetic acid, trifluoroacetic acid, or trifluoromethanesulfonic acid.

[0018] Preferably, the solvent is acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water.

[0019] Compared with the prior art, the present invention has the following beneficial effects: This invention utilizes readily available and inexpensive unsaturated hydrocarbons and sulfur sources as raw materials, and readily available and inexpensive phosphine catalysts as organic photocatalysts, achieving a separation yield of up to 92% for the synthesis of dialkyl sulfide compounds. Compared with traditional processes, this invention has advantages such as readily available and inexpensive raw materials, mild conditions, simple operation, high atom economy, good functional group compatibility, good biocompatibility, and broad substrate universality. It is suitable for the industrial production of dialkyl sulfide compounds, especially complex sulfide compounds containing multiple functional groups.

[0020] Furthermore, the present invention is applicable not only to simple olefins, but also to dienes and complex olefins derived from drug molecules, with a broad substrate range.

[0021] Furthermore, the sulfur source described in this invention is sodium sulfide, hydrogen sulfide, thiol, or dithiol. Therefore, not only can symmetrical dialkyl sulfides be synthesized efficiently from sodium sulfide, hydrogen sulfide, or dithiol, but asymmetrical dialkyl sulfides can also be synthesized efficiently from thiol.

[0022] Furthermore, the present invention exhibits good reactivity in both buffer solutions and water, and has good biocompatibility. Therefore, the solvent can be selected from acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water. Detailed Implementation

[0023] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0024] It should be noted that the process equipment or apparatus not specifically mentioned in the following embodiments are all conventional equipment or apparatus in the art.

[0025] It should be noted that the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to these processes, methods, products, or apparatuses. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not intended to limit the order of the method steps or define the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0026] The method for synthesizing dialkyl sulfide compounds according to the present invention includes: using unsaturated hydrocarbons and sulfur sources as raw materials, using a phosphine catalyst as a photocatalyst, and carrying out a reaction in a solvent and under inert gas protection, under blue light irradiation to obtain dialkyl sulfide compounds.

[0027] Mechanistic studies have shown that the active catalyst for the reaction is a pentavalent phosphine salt (the cation part of Formula 6) generated in situ from a phosphine catalyst. Its spectral absorption extends to approximately 480 nm, and it can be excited throughout the absorption spectral region, catalyzing the reaction of unsaturated hydrocarbons and sulfur sources to yield dialkyl sulfide compounds. Since visible light is a green energy source, blue light (400–480 nm) is preferred for driving the reaction.

[0028] In some preferred embodiments of the present invention, the unsaturated hydrocarbon is an olefin or an alkyne, wherein the structural formula of the olefin is shown in formula (1) or formula (2), and the structural formula of the alkyne is shown in formula (3):

[0029] R1, R2 and R3 are each independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, ester group, or R2 and R3 are connected to form a cycloalkyl or substituted cycloalkyl; R4 is selected from oxygen, alkyl, substituted alkyl, substituted amino group, phthalic acid group; R5 and R6 are each independently selected from hydrogen, alkyl, aryl, substituted aryl.

[0030] For example, the olefin is 1-allyl-2-methoxybenzene, allyl phenyl carbonate, 1-allylbenzotriazole, vinyl benzoate, vinyl acetate, allyl ether, 9-bromo-1-nonene, 4-allyl anisole, styrene, diallyl phthalate, but-3-en-1-yl(4-chlorophenyl) sulfide, diethyl allyl malonate, diethyl diallyl malonate, 3-methylbut-3-enyl benzoate, 3-cyclohexanediol. Dimethyl pentene-1,1-dicarboxylate, N,N-diallylcarbamate tert-butyl ester, N,N-diallyl-4-methylbenzenesulfonamide, N,N-diallyl-3-bromo-4-chlorobenzenesulfonamide, allyl-tetra-O-acetyl-β-D-glucopyranoside, N-(4-phenylthiazol-2-yl)hept-6-enamide, 3-allyl-3-toluenesulfonylhex-5-en-2-one, pent-4-en-1-yl-4-( (1,1'-Biphenyl)-4-yl)-4-oxobutyrate, pent-4-en-1-yl 2-(4-(2-(4-chlorobenzoamido)ethyl)phenoxy)-2-methylpropionate, pent-4-en-1-yl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate, 3-(4-isobutylphenyl)propionate 3-methylbut-3-en-1-yl ester, 3-methylbut- One of 3-en-1-yl 2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazolyl-5-carboxylic acid ester, (1r,4R)-N-((R)-1-(diallylamino)-1-oxo-3-phenylpropane-2-yl)-4-isopropylcyclohexane-1-carboxamide, and 4-chloro-N-(4-((1-(diallylamino)-2-methyl-1-oxopropane-2-yl)oxy)phenethyl)benzamide.

[0031] For example, the alkyne is 1-ethynyl-4-methylbenzene.

[0032] In some preferred embodiments of the present invention, the sulfur source is sodium sulfide, hydrogen sulfide, thiols, or dithiols; when the sulfur source is sodium sulfide or hydrogen sulfide, the method further includes: using an organic acid as an additive, and carrying out the reaction under blue light irradiation in the presence of the additive. The organic acid reacts with sodium sulfide or hydrogen sulfide to produce active sulfur species.

[0033] For example, the organic acid is formic acid, acetic acid, trifluoroacetic acid, or trifluoromethanesulfonic acid.

[0034] In some preferred embodiments of the present invention, the thiol has the structural formula shown in formula (4), and the dithiol has the structural formula shown in formula (5):

[0035] R7 is selected from alkyl, substituted alkyl, aryl, substituted aryl, and glycosyl; R8 is an alkyl group.

[0036] For example, the thiol is benzyl thiol, 4-methylthiophenol, N-acetyl-L-cysteine ​​methyl ester, thiobenzoic acid, 1-thio-β-D-glucose tetraacetate, 1-thio-β-D-glucose tetraacetate, thioacetic acid, or pentafluoropentanethiol; the dithiol is 1,2-ethanedithiol or 1,2-propanedithiol.

[0037] When the sulfur source is sodium sulfide, the preferred phosphine catalyst is 1,1'-binaphthyl-2,2'-bis(diphenylphosphine) as shown in formula (7). In this case, if the phosphine salt shown in formula (6) is used as the phosphine catalyst, the product yield is lower than that of using BINAP as the phosphine catalyst. When the sulfur source is hydrogen sulfide, thiol, or dithiol, the phosphine catalyst is 1,1'-binaphthyl-2,2'-bis(diphenylphosphine) as shown in formula (7) or the phosphine salt shown in formula (6) ([P]). + [X] - );

[0038] Where X is Cl — or Br — .

[0039] In some preferred embodiments of the present invention, the solvent is acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water. When the sulfur source is sodium sulfide or hydrogen sulfide, the solvent is more preferably acetonitrile, water, acetone, diethyl ether, or dichloromethane. When the sulfur source is thiol or dithiol, the solvent is more preferably acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water.

[0040] In some specific embodiments of the present invention, the unsaturated hydrocarbon is an olefin as shown in formula (1) or formula (2), the sulfur source is sodium sulfide, and the synthesis method is specifically as follows: sodium sulfide, BINAP, olefin and organic acid are added to a solvent and reacted under inert gas protection and blue light irradiation to obtain a dialkyl sulfide compound as shown in formula (8) or formula (9); wherein, the molar ratio of BINAP, organic acid, sodium sulfide and olefin is preferably (0.1~0.25):(5~15):(1~2):1, the solvent is acetonitrile, water, acetone, diethyl ether or dichloromethane, preferably acetonitrile, the reaction temperature is room temperature, and the reaction time is 6~72 h; The reaction formula is as follows: .

[0041] In some specific embodiments of the present invention, the unsaturated hydrocarbon is an olefin as shown in formula (1) or formula (2), the sulfur source is hydrogen sulfide, and the synthesis method is specifically as follows: adding hydrogen sulfide, BINAP or phosphine salt (formula (6)), olefin and organic acid to a solvent, reacting under inert gas protection and blue light irradiation to obtain a dialkyl sulfide compound as shown in formula (8) or formula (9); wherein, when BINAP is used as a photocatalyst, the molar ratio of BINAP, organic acid, hydrogen sulfide and olefin is preferably (0.1~0.25):(5~15):(1~2):1, and when the phosphine salt shown in formula (6) is used as a photocatalyst, the molar ratio of phosphine salt, organic acid, hydrogen sulfide and olefin is preferably (0.1~0.25):(2~10):(1~5):1; the solvent is acetonitrile, water, acetone, diethyl ether or dichloromethane, preferably acetonitrile, the reaction temperature is room temperature, and the reaction time is 6~72 h; The reaction formula is as follows: .

[0042] In some specific embodiments of the present invention, the unsaturated hydrocarbon is an olefin represented by formula (1) or formula (2) or an alkyne represented by formula (3), the sulfur source is a thiol represented by formula (4), and the synthesis method is specifically as follows: adding a phosphine catalyst (BINAP or phosphine salt), an olefin or alkyne, and a thiol to a solvent, reacting under inert gas protection and blue light irradiation to obtain a dialkyl sulfide compound; in this method, the molar ratio of the phosphine catalyst, the thiol, and the olefin or alkyne is (0.01~0.15):(1~2):1; the solvent is acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water, preferably acetonitrile, the reaction temperature is room temperature, and the reaction time is 6~24 h; The reaction formulas for the alkenes represented by formula (1) or the alkynes represented by formula (3) with the thiols represented by formula (4) are as follows: .

[0043] The reaction formulas for the olefins shown in formula (2) and the thiols shown in formula (4) can be referred to the above reaction formulas and will not be listed one by one.

[0044] In some specific embodiments of the present invention, the unsaturated hydrocarbon is an olefin as shown in formula (2), the sulfur source is a dithiol as shown in formula (5), and the synthesis method is as follows: a phosphine catalyst (BINAP or phosphine salt), an olefin, and a dithiol are added to a solvent and reacted under inert gas protection and blue light irradiation to obtain a dialkyl sulfide compound as shown in formula (12); in this method, the molar ratio of the phosphine catalyst, the thiol, and the olefin is (0.01~0.15):(1~2):1; the solvent is acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water, preferably acetonitrile, the reaction temperature is room temperature, and the reaction time is 6~24 h; The reaction formula is as follows: .

[0045] It should be noted that alkynes do not react well with sodium sulfide, hydrogen sulfide, or dithiol. Therefore, when the unsaturated hydrocarbon is an alkyne as shown in formula (3), the sulfur source is preferably a thiol as shown in formula (4). Alkenes as shown in formula (1) do not react well with dithiol. Therefore, when the unsaturated hydrocarbon is an alkene as shown in formula (1), the sulfur source is preferably sodium sulfide, hydrogen sulfide, or thiol.

[0046] Example 1

[0047] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 31 μL of 1-allyl-2-methoxybenzene (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 25.7 mg of pure product in 78% yield.

[0048] 1 H NMR (400 MHz, CDCl3)δ 7.23 – 7.12 (m, 4H), 6.89 (ddd, J = 13.5, 9.9,4.6 Hz, 4H), 3.82 (s, 6H), 2.78 – 2.68 (m, 4H), 2.60 – 2.51 (m, 4H), 1.95 –1.82 (m, 4H); 13C NMR (100 MHz, CDCl3)δ 157.56, 130.15, 130.06, 127.23, 120.44,110.31, 55.31, 31.81, 29.71, 29.65; HRMS (LCMS-ESI)m / z Calcd. for C 20 H 27 O2S [M+H] + 331.1726, found: 331.1733. Example 2

[0049] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 33 μL of allyl phenyl carbonate (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 33.2 mg of pure product in 85% yield.

[0050] 1 H NMR (400 MHz, CDCl3)δ 7.42 – 7.34 (m, 4H), 7.27 – 7.21 (m, 2H),7.20 – 7.15 (m, 4H), 4.36 (t, J = 6.3 Hz, 4H), 2.68 (t, J = 7.2 Hz, 4H), 2.09 –1.99 (m, 4H); 13 C NMR (100 MHz, CDCl3)δ 153.75, 151.19, 129.62, 126.19, 121.14,67.29, 28.64, 28.41; HRMS (LCMS-ESI)m / z Calcd. for C 20 H 22 O6SNa [M+Na] + 413.1029, found: 413.1020. Example 3

[0051] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 39.6 mg of but-3-en-1-yl(4-chlorophenyl) sulfide (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 72 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 29.0 mg of pure product, with a yield of 67%.

[0052] 1 H NMR (400 MHz, CDCl3)δ 7.24 (s, 8H), 2.93 – 2.86 (m, 4H), 2.49 (dd, J = 9.0, 4.6 Hz, 4H), 1.78 – 1.64 (m, 8H); 13 C NMR (100 MHz, CDCl3)δ 135.22, 131.97, 130.58, 129.12, 33.63,31.65, 28.58, 28.16; HRMS (LCMS-ESI)m / z Calcd. for C 20 H 24 Cl2S3[M+Na] + 453.0309, found: 453.0343. Example 4

[0053] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 29 μL of 1-allylbenzotriazole (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 72 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 25.3 mg of pure product, with a yield of 72%.

[0054] 1 H NMR (400 MHz, CDCl3)δ 8.05 (d, J = 8.4 Hz, 2H), 7.55 (d, J = 8.3 Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 4.75 (t, J = 6.6 Hz, 4H), 2.51 (t, J = 6.9 Hz, 4H), 2.27 (p, J = 6.7 Hz, 4H); 13 C NMR (100 MHz, CDCl3)δ 146.05, 133.19, 127.55, 124.10, 120.20,109.33, 46.42, 29.20, 29.00; HRMS (LCMS-ESI)m / z Calcd. for C 18 H 21 N6S [M+H] + 353.1543, found: 353.1547. Example 5

[0055] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 41 μL of diethyl allyl malonate (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 27.6 mg of pure product in 64% yield.

[0056] 1 H NMR (400 MHz, CDCl3)δ 4.22 – 4.14 (m, 8H), 3.31 (t, J = 7.5 Hz, 2H), 2.50 (t, J = 7.3 Hz, 4H), 2.02 – 1.92 (m, 4H), 1.66 – 1.55 (m, 4H), 1.25 (t, J =7.1 Hz, 12H); 13 C NMR (100 MHz, CDCl3)δ 169.34, 61.49, 51.69, 31.55, 27.94, 27.28,14.18; HRMS (LCMS-ESI)m / z Calcd. for C 20 H 34 O8SNa [M+Na] + 457.1867, found: 457.1867. Example 6

[0057] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 38 mg of 3-methylbut-3-enylbenzoate (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 29.4 mg of pure product in 71% yield.

[0058] 1 H NMR (400 MHz, CDCl3)δ 8.07 – 8.00 (m, 4H), 7.54 (t, J = 7.4 Hz, 2H), 7.43 (t, J = 7.6 Hz, 4H), 4.46 – 4.29 (m, 4H), 2.56 (dd, J = 12.6, 6.1 Hz, 2H), 2.46 (dd, J = 12.3, 6.8 Hz, 2H), 1.99 (dt, J = 20.3, 6.8 Hz, 2H), 1.89 (td, J =13.2, 6.6 Hz, 2H), 1.63 (td, J = 13.4, 6.5 Hz, 2H), 1.07 (d, J = 6.6 Hz, 6H); 13 C NMR (100 MHz, CDCl3)δ 166.69, 133.01, 130.45, 129.66, 128.47,63.22, 40.61, 40.55, 34.80, 30.78, 30.75, 19.50; HRMS (LCMS-ESI)m / z Calcd. for C 24 H 30 O4SNa [M+Na] + 437.1757, found: 437.1759. Example 7

[0059] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 37 mg (0.2 mmol, 1.0 equiv.) of dimethyl 3-cyclopentene-1,1-dicarboxylate were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 48 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 20.1 mg of pure product, with a yield of 50%.

[0060] 1 H NMR (400 MHz, CDCl3)δ 3.72 (s, 12H), 3.25 – 3.13 (m, 2H), 2.72 (dd, J = 13.6, 7.3 Hz, 2H), 2.51 – 2.39 (m, 2H), 2.20 – 2.02 (m, 6H), 1.71 – 1.58(m, 2H); 13 C NMR (100 MHz, CDCl3)δ 172.75, 172.25, 59.82, 53.00, 52.95, 43.24,43.13, 42.15, 42.10, 33.80, 33.68, 33.48; HRMS (LCMS-ESI)m / z Calcd. for C 18 H 26 O8SNa [M+Na] + 425.1241, found: 425.1229. Example 8

[0061] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 28 μL of vinyl benzoate (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was carried out at room temperature under blue light with stirring for 24 h. After the reaction was completed, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 24.3 mg of pure product, with a yield of 74%.

[0062] 1 H NMR (400 MHz, CDCl3)δ 8.04 (d, J = 7.9 Hz, 4H), 7.56 (t, J = 7.3 Hz, 2H), 7.43 (t, J = 7.7 Hz, 4H), 4.52 (t, J = 6.8 Hz, 4H), 2.99 (t, J = 6.8 Hz, 4H); 13 C NMR (100 MHz, CDCl3)δ 166.45, 133.22, 130.02, 129.76, 128.53,64.05, 30.95; HRMS (LCMS-ESI)m / z Calcd. for C 18 H 18 O4SNa [M+Na] + 353.0818, found: 353.0822. Example 9

[0063] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 19 μL of vinyl acetate (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the mixture was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 15.2 mg of pure product, with a yield of 74%.

[0064] 1 H NMR (400 MHz, CDCl3)δ 4.23 (t, J = 6.8 Hz, 4H), 2.79 (t, J = 6.8 Hz, 4H), 2.07 (s, 6H); 13 C NMR (100 MHz, CDCl3)δ 170.92, 63.53, 30.85, 21.00; HRMS (LCMS-ESI)m / z Calcd. for C8H 14 O4SNa [M+Na] + 229.0505, found: 229.0516. Example 10

[0065] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 86.0 mg (0.2 mmol, 1.0 equiv.) of pent-4-en-1-yl 2-(4-(2-(4-chlorobenzamido)ethyl)phenoxy)-2-methylpropionate were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 62.8 mg of pure product (70% yield).

[0066] 11H NMR (400 MHz, CDCl3) δ 7.64 – 7.57 (m, 4H), 7.36 – 7.29 (m, 4H), 7.04 (d, J J = 8.5 Hz, 4H), 6.77 (t, J J = 5.7 Hz, 4H), 6.42 (t, J J = 5.5 Hz, 2H), 4.13 (t, J J = 6.6 Hz, 4H), 3.60 (dd, J J = 13.0, 6.9 Hz, 4H), 2.82 (t, J J = 7.0 Hz, 4H), 2.40 (t, J J = 7.3 Hz, 4H), 1.65 – 1.47 (m, 20H), 1.38 – 1.28 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 174.38, 166.52, 154.16, 137.61, 133.06, 132.45, 129.51, 128.79, 128.40, 119.39, 79.19, 65.30, 41.38, 34.78, 31.95, 29.16, 28.13, 25.46, 25.10; HRMS (LCMS-ESI) m / z Calcd. for C 48 21H 59 Cl2N2O8S [M+H] + 893.3364, found: 893.3365. Example 11

[0067] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv), 18.7 mg of BINAP (0.03 mmol, 0.15 equiv), and 64.5 mg of pent-4-en-1-yl 4-((1,1'-biphenyl)-4-yl)-4-oxobutyrate (0.2 mmol, 1.0 equiv) were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL of formic acid (2.0 mmol, 10.0 equiv) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 54.1 mg of pure product, with a yield of 80%.

[0068] 1 H NMR (400 MHz, CDCl3)δ 8.05 (d, J = 8.4 Hz, 4H), 7.69 (d, J = 8.4 Hz,4H), 7.65 – 7.60 (m, 4H), 7.47 (dd, J = 10.2, 4.7 Hz, 4H), 7.42 – 7.37 (m, 2H), 4.11 (t, J = 6.6 Hz, 4H), 3.34 (t, J = 6.6 Hz, 4H), 2.78 (t, J = 6.6 Hz, 4H), 2.49(t, J = 7.3 Hz, 4H), 1.70 – 1.55 (m, 8H), 1.51 – 1.39 (m, 4H); 13 C NMR (100 MHz, CDCl3)δ 197.79, 173.05, 145.95, 139.91, 135.36,129.05, 128.73, 128.34, 127.35, 127.34, 64.68, 33.51, 32.06, 29.37, 28.42,28.35, 25.33; HRMS (LCMS-ESI)m / z Calcd. for C 42 H 46 O6SNa [M+Na] + 701.2907, found: 701.2904. Example 12

[0069] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 85.2 mg (0.2 mmol, 1.0 equiv.) of pent-4-en-1-yl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 50.2 mg of pure product (57% yield).

[0070] 1 H NMR (400 MHz, CDCl3)δ 7.65 (d, J = 8.4 Hz, 4H), 7.46 (d, J = 8.4 Hz, 4H), 6.96 (d, J = 2.4 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 6.66 (dd, J = 9.0, 2.5 Hz, 2H), 4.09 (t, J = 6.6 Hz, 4H), 3.82 (s, 6H), 3.65 (s, 4H), 2.42 (t, J = 7.3 Hz, 4H), 2.38 (s, 6H), 1.67 – 1.58 (m, 4H), 1.54 (dt, J = 14.9, 7.4 Hz, 4H), 1.43 –1.33 (m, 4H); 13C NMR (100 MHz, CDCl3)δ 171.00, 168.36, 156.11, 139.33, 135.99,134.01, 131.27, 130.89, 130.76, 129.21, 115.04, 112.77, 111.67, 101.45,64.96, 55.79, 32.02, 30.50, 29.26, 28.34, 25.26, 13.47; HRMS (LCMS-ESI)m / z Calcd. for C 48 H 54 Cl2N3O8S [M+NH4] + 902.3003, found: 902.2996. Example 13

[0071] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 54.9 mg (0.2 mmol, 1.0 equiv.) of 3-methylbut-3-en-1-yl 2-(4-isobutylphenyl)propionate were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 35.8 mg of pure product in 61% yield.

[0072] 1 H NMR (400 MHz, CDCl3)δ 7.19 (d, J = 7.9 Hz, 4H), 7.09 (d, J = 8.0 Hz,4H), 4.17 – 4.04 (m, 4H), 3.68 (q, J = 7.1 Hz, 2H), 2.48 – 2.35 (m, 6H), 2.34 –2.25 (m, 2H), 1.91 – 1.72 (m, 4H), 1.71 – 1.60 (m, 2H), 1.52 – 1.40 (m, 8H), 0.97 – 0.86 (m, 18H); 13C NMR (100 MHz, CDCl3)δ 174.86, 140.60, 137.91, 137.88, 129.42,127.26, 62.99, 62.93, 45.30, 45.16, 40.46, 34.63, 30.61, 30.50, 30.31, 22.51,19.32, 19.29, 18.59; HRMS (LCMS-ESI)m / z Calcd. for C 36 H 54 O4SNa [M+Na] + 605.3635 found: 605.3626. Example 14

[0073] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 76.9 mg (0.2 mmol, 1.0 equiv.) of 3-methylbut-3-en-1-yl-2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazolyl-5-carboxylic acid ester were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 38.6 mg of pure product in 48% yield.

[0074] 1 H NMR (400 MHz, CDCl3)δ 8.13 (d, J = 2.3 Hz, 2H), 8.05 (dd, J = 8.8, 2.3Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 4.42 – 4.25 (m, 4H), 3.88 (d, J = 6.5 Hz, 4H), 2.74 (s, 6H), 2.51 (dddd, J = 32.4, 12.6, 6.5, 1.9 Hz, 4H), 2.18 (dp, J = 13.3, 6.6 Hz, 2H), 1.97 (td,J = 12.5, 5.8 Hz, 2H), 1.87 (td, J = 13.2, 6.6 Hz, 2H), 1.62 (td, J = 13.9, 6.4 Hz, 2H), 1.08 (d, J = 6.7 Hz, 18H); 13 C NMR (100 MHz, CDCl3)δ 167.26, 162.56, 162.04, 161.30, 132.60,132.09, 126.00, 121.74, 115.45, 112.70, 103.01, 75.77, 63.55, 40.45, 34.68,30.69, 30.67, 28.23, 19.52, 19.13, 17.59; HRMS (LCMS-ESI)m / z Calcd. for C 42 H 51 N4O6S3[M+H] + 803.2965, found: 803.2970. Example 15

[0075] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide and 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL (2.0 mmol, 10.0 equiv.) of formic acid, and 49 μL (0.2 mmol, 1.0 equiv.) of diallyl malonate were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 37.7 mg of pure product, with a yield of 73%.

[0076] 1 H NMR (400 MHz, CDCl 3, Major isomer)δ 4.16 (q, J= 7.0 Hz, 8H), 2.58 –2.48 (m, 2H), 2.48 – 2.33 (m, 6H), 2.28 – 2.16 (m, 4H), 2.14 – 2.04 (m, 2H), 1.99 (dd, J = 13.7, 5.0 Hz, 2H), 1.23 (t, J = 7.1 Hz, 12H), 0.87 (d, J = 6.8 Hz, 6H); 13 C NMR (100 MHz, CDCl3)δ 172.94, 172.83, 61.53, 61.51, 58.96, 42.45,42.40, 41.39, 38.32, 35.89, 35.85, 33.33, 33.32, 14.79, 14.78, 14.16; HRMS (LCMS-ESI)m / z Calcd. for C 26 H 42 O8SNa [M+Na] + 537.2493, found: 537.2491. Example 16

[0077] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 51 μL of 3-allyl-3-toluenesulfonylhex-5-en-2-one (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 37.4 mg of pure product, with a yield of 60%.

[0078] 1 H NMR (400 MHz, CDCl3)δ 7.59 (d, J = 6.7 Hz, 4H), 7.30 (d, J= 7.0 Hz,4H), 2.60 – 2.24 (m, 22H), 2.15 – 1.96 (m, 6H), 0.96 (d, J = 3.8 Hz, 6H); 13 C NMR (100 MHz, CDCl3)δ 202.54, 145.38, 133.43, 129.77, 129.52,82.76, 41.51, 37.59, 35.36, 35.26, 35.07, 33.18, 27.79, 21.81, 15.22; HRMS (LCMS-ESI)m / z Calcd. for C 32 H 42 O6S3Na [M+Na] + 641.2036, found: 641.2053. Example 17

[0079] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 25 μL of allyl ether (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the mixture was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 16.3 mg of pure product, with a yield of 71%.

[0080] 1 H NMR (400 MHz, CDCl3)δ 3.97 (ddd, J = 23.4, 13.7, 6.8 Hz, 6H), 3.64 –3.51 (m, 3H), 3.47 (dd, J = 7.9, 4.1 Hz, 2H), 3.33 (t, J = 7.6 Hz, 1H), 2.76 –2.57 (m, 3H), 2.53 – 2.30 (m, 7H), 2.05 – 1.89 (m, 2H), 1.06 (d, J= 6.0 Hz, 3H), 0.98 (d, J = 6.3 Hz, 6H); 13 C NMR (100 MHz, CDCl3)δ 75.35, 75.15, 73.35, 71.97, 47.04, 42.27,39.91, 36.12, 36.09, 35.85, 35.77, 31.43, 31.40, 31.38, 31.34, 17.20, 12.89; HRMS (LCMS-ESI)m / z Calcd. for C 12 H 23 O2S [M+H] + 231.1413, found: 231.1424. Example 18

[0081] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 42 μL of N,N-diallylcarbamate tert-butyl ester (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 28.3 mg of pure product in 66% yield.

[0082] 1 H NMR (400 MHz, CDCl3)δ 3.75 – 3.30 (m, 7H), 3.15 – 2.95 (m, 5H), 2.92 – 2.76 (m, 2H), 2.70 (d, J = 11.0 Hz, 2H), 2.53 (s, 1.5H), 2.45 – 2.20 (m, 6.5H), 1.87 (s, 4H), 1.40 (s, 31H), 1.00 (s, 6H), 0.90 (s, 4H); 13C NMR (100 MHz, CDCl3)δ 154.73, 154.40, 79.18, 53.23, 53.10, 52.79,52.55, 51.39, 51.05, 49.35, 49.00, 45.81, 45.20, 41.74, 41.15, 38.40, 37.72,35.09, 34.83, 34.44, 31.90, 28.56, 16.46, 13.26; HRMS (LCMS-ESI)m / z Calcd. for C 22 H 40 N₂O₄SNa [M+Na] + 451.2601, found: 451.2603. Example 19

[0083] To a 10 mL Schlenk reaction tube, 23.4 mg of sodium sulfide (0.3 mmol, 1.5 equiv.) and 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 75 μL of formic acid (2.0 mmol, 10.0 equiv.), and 47 μL of N,N-diallyl-4-methylbenzenesulfonamide (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 44.5 mg of pure product in 83% yield.

[0084] 1 H NMR (400 MHz, CDCl3)δ 7.72 – 7.65 (m, 5.7H), 7.31 (d, J = 7.9 Hz, 5.7H), 3.47 (dd, J = 9.9, 7.4 Hz, 1.8H), 3.36 (td, J = 9.9, 6.6 Hz, 4H), 3.09(ddd, J = 10.3, 7.0, 3.5 Hz, 2H), 3.02 – 2.93 (m, 2.9H), 2.77 (dd, J= 9.7, 8.1Hz, 0.9H), 2.54 – 2.48 (m, 0.9H), 2.44 – 2.36 (m, 10.5H), 2.26 – 2.18 (m,2H), 2.17 – 2.04 (m, 4H), 1.85 – 1.70 (m, 1.7H), 0.90 (d, J = 6.5 Hz, 2.6H), 0.74 (d, J = 7.0 Hz, 6H); 13 C NMR (100 MHz, CDCl3) δ1H NMR (101 MHz, CDCl3) δ 143.61, 143.53,134.02, 133.67, 129.78, 127.65, 127.54, 54.78, 54.48, 52.82, 51.08, 45.59,45.56, 41.75, 41.70, 38.49, 35.34, 34.93, 34.81, 31.38, 31.32, 31.16, 21.65,16.85, 13.05; HRMS (LCMS-ESI)m / z Calcd. for C 26 H 37 N₂O₄S₃[M+H] + 537.1910, found: 537.1913. Example 20

[0085] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 70.1 mg (0.2 mmol, 1.0 equiv.) of N,N-diallyl-3-bromo-4-chlorobenzenesulfonamide were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 57.4 mg of pure product (78% yield).

[0086] 1 H NMR (400 MHz, CDCl3)δ 7.90 (d, J= 2.0 Hz, 3H), 7.79 (d, J = 8.3 Hz, 3H), 7.56 (dd, J = 8.2, 1.9 Hz, 3H), 3.50 (dd, J = 12.4, 4.6 Hz, 2H), 3.38 (dt, J = 6.4, 5.0 Hz, 4H), 3.17 (dd, J = 9.7, 6.8 Hz, 2H), 3.02 (dd, J = 9.3, 4.4 Hz, 3H), 2.81 (t, J = 8.7 Hz, 1H), 2.63 – 2.52 (m, 1H), 2.50 – 2.38 (m, 2H), 2.30 (dd, J = 11.8, 6.1 Hz, 2H), 2.26 – 2.08 (m, 5H), 1.94 – 1.75 (m, 2H), 0.96 (d, J = 6.4 Hz, 3H), 0.88 – 0.76 (m, 6H); 13 C NMR (100 MHz, CDCl3) δ 137.87, 137.60, 135.90, 134.60, 129.07, 129.00, 127.99, 127.89, 126.53, 126.43, 54.82, 54.49, 52.77, 51.12, 45.63, 45.59, 41.82, 41.77, 38.56, 35.52, 35.48, 34.83, 34.72, 31.44, 31.37, 31.23, 16.73, 13.06, 13.03; HRMS (LCMS-ESI) m / z Calcd. for C 24 H 29 Br2Cl2N2O4S3 [M+H] + 732.9028, found: 732.9030. Example 21

[0087] To a 10 mL Schlenk reaction tube, 23.4 mg (0.3 mmol, 1.5 equiv.) of sodium sulfide, 18.7 mg (0.03 mmol, 0.15 equiv.) of BINAP, and 79.3 mg (0.2 mmol, 1.0 equiv.) of (1r,4R)-N-((R)-1-(dipropenylamino)-1-oxo-3-phenylpropane-2-yl)-4-isopropylcyclohexane-1-carboxamide were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 75 μL (2.0 mmol, 10.0 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 46.1 mg of pure product in 58% yield.

[0088] 1 H NMR (400 MHz, CDCl3)δ 7.24 (d, J = 20.9 Hz, 10H), 6.35 (d, J = 7.5 Hz, 2H), 4.87 (s, 2H), 3.82 – 3.27 (m, 4H), 3.16 (d, J = 9.6 Hz, 1H), 2.98 (dd, J =24.8, 9.2 Hz, 5H), 2.88 – 2.60 (m, 1H), 2.58 – 2.11 (m, 6H), 2.02 (t, J = 11.7Hz, 3H), 1.90 (d, J = 12.2 Hz, 4H), 1.78 (d, J = 11.6 Hz, 6H), 1.40 (t, J = 12.4Hz, 6H), 1.10 – 0.91 (m, 8H), 0.82 (dd, J = 30.0, 6.4 Hz, 14H), 0.63 (dd, J =24.3, 5.2 Hz, 2H); 13C NMR (100 MHz, CDCl3)δ 175.70, 170.20, 136.53, 129.62, 128.65,128.52, 127.12, 77.48, 77.16, 76.84, 51.89, 51.76, 45.67, 45.65, 43.40,39.89, 32.92, 29.96, 29.63, 29.17, 29.07, 19.89; HRMS (LCMS-ESI)m / z Calcd. for C 50 H 75 N4O4S [M+H] + 827.5504, found: 827.5512. Example 22

[0089] Method 1: 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) was added to a 10 mL Schlenk reaction tube. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 34 μL of 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 50 μL of benzyl mercaptan (0.4 mmol, 2.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 49.9 mg of pure product (92% yield).

[0090] To verify the biocompatibility of the reaction system, PBS buffer, glycine, L-proline, L-tyrosine methyl ester, Boc-L-leucine, Boc-L-proline, Boc-L-valine, and Boc-L-isoleucine were introduced into the experiment. Specifically, the following experiments were conducted: Method 2: Add 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) to a 10 mL Schlenk reaction tube. Under N2 conditions, add PBS buffer (pH = 7.0, 1.0 mL), 34 μL of 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 50 μL of benzyl mercaptan (0.4 mmol, 2.0 equiv.) sequentially. Stir the reaction under blue light at room temperature for 24 h. After the reaction, extract with ethyl acetate, remove the solvent by vacuum distillation, and separate by preparative thin-layer chromatography to obtain 48.2 mg of pure product, with a yield of 89%.

[0091] Method 3: Add 18.7 mg BINAP (0.03 mmol, 0.15 equiv.) and 30 mg glycine (0.4 mmol, 2.0 equiv.) to a 10 mL Schlenk reaction tube. Under N2 conditions, add PBS buffer (pH = 7.0, 1.0 mL), 34 μL 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 50 μL benzyl mercaptan (0.4 mmol, 2.0 equiv.) sequentially. Stir the reaction under blue light at room temperature for 24 h. After the reaction, extract with ethyl acetate, remove the solvent by vacuum distillation, and separate by preparative thin-layer chromatography to obtain 49.5 mg of pure product, with a yield of 91%.

[0092] Method 4: Add 18.7 mg BINAP (0.03 mmol, 0.15 equiv.) and 46 mg L-proline (0.4 mmol, 2.0 equiv.) to a 10 mL Schlenk reaction tube. Under N2 conditions, add PBS buffer (pH = 7.0, 1.0 mL), 34 μL 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 50 μL benzyl mercaptan (0.4 mmol, 2.0 equiv.) sequentially. Stir the reaction under blue light at room temperature for 24 h. After the reaction, extract with ethyl acetate, remove the solvent by vacuum distillation, and separate by preparative thin-layer chromatography to obtain 48.7 mg of pure product, with a yield of 89%.

[0093] Method 5: Add 18.7 mg BINAP (0.03 mmol, 0.15 equiv.) and 78 mg L-tyrosine methyl ester (0.4 mmol, 2.0 equiv.) to a 10 mL Schlenk reaction tube. Under N2 conditions, add PBS buffer (pH = 7.0, 1.0 mL), 34 μL 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 50 μL benzyl mercaptan (0.4 mmol, 2.0 equiv.) sequentially. Stir the reaction under blue light at room temperature for 24 h. After the reaction, extract with ethyl acetate, remove the solvent by vacuum distillation, and separate by preparative thin-layer chromatography to obtain 49 mg of pure product, with a yield of 90%.

[0094] Method 6: Add 18.7 mg BINAP (0.03 mmol, 0.15 equiv.), 11.6 mg Boc-L-leucine (0.05 mmol), 10.8 mg Boc-L-proline (0.05 mmol), 10.9 mg Boc-L-valine (0.05 mmol), and 11.6 mg Boc-L-isoleucine (0.05 mmol) to a 10 mL Schlenk reaction tube. Under N2 conditions, add PBS buffer (pH = 7.0, 1.0 mL), 34 μL 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 50 μL benzyl mercaptan (0.4 mmol, 2.0 equiv.) sequentially. Stir the reaction under blue light at room temperature for 24 h. After the reaction was completed, the product was extracted with ethyl acetate, the solvent was removed by vacuum distillation, and the product was separated by preparative thin-layer chromatography to obtain 50 mg of pure product, with a yield of 92%.

[0095] The products obtained by the above six methods are consistent: 1 H NMR (400 MHz, CDCl3)δ 7.31 – 7.24 (m, 4H), 7.24 – 7.19 (m, 1H), 7.07 – 7.01 (m, 2H), 6.83 – 6.77 (m, 2H), 3.77 (s, 3H), 3.68 (s, 2H), 2.64 –2.56 (m, 2H), 2.44 – 2.36 (m, 2H), 1.88 – 1.77 (m, 2H); 13 C NMR (100 MHz, CDCl3)δ 157.91, 138.67, 133.70, 129.45, 128.93,128.55, 126.97, 113.86, 55.34, 36.28, 33.94, 31.12, 30.68; HRMS (LCMS-APCl)m / z Calcd. for C 17 H 21 OS [M+H] + 273.1308, found: 273.1293. Example 23

[0096] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) and 50 mg of 4-methylthiophenol (0.4 mmol, 2.0 equiv.) were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 24 μL of styrene (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 36.7 mg of pure product, with a yield of 80%.

[0097] 1 H NMR (400 MHz, CDCl3)δ 7.29 (dd, J = 9.7, 4.6 Hz, 4H), 7.23 – 7.15 (m,3H), 7.10 (d, J = 7.9 Hz, 2H), 3.11 (dd, J = 9.0, 6.7 Hz, 2H), 2.89 (dd, J = 9.0,6.8 Hz, 2H), 2.32 (s, 3H); 13 C NMR (100 MHz, CDCl3)δ 140.43, 136.28, 132.59, 130.20, 129.83,128.61, 128.58, 126.49, 35.92, 35.86, 21.13; HRMS (LCMS-ESI)m / z Calcd. for C 15 H 16 S [M] + 228.0967, found: 228.0992. Example 24

[0098] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) and 73 mg of N-acetyl-L-cysteine ​​methyl ester (0.4 mmol, 2.0 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 24 μL of styrene (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 46.8 mg of pure product, with a yield of 83%.

[0099] 1 H NMR (400 MHz, CDCl3)δ 7.33 – 7.26 (m, 2H), 7.22 (t, J = 4.8 Hz, 1H),7.20 – 7.15 (m, 2H), 6.43 (d, J = 7.1 Hz, 1H), 4.82 (dt, J = 7.6, 5.1 Hz, 1H), 3.74 (s, 3H), 2.99 (qd, J = 13.9, 5.1 Hz, 2H), 2.85 (dt, J = 8.6, 2.4 Hz, 2H),2.80 – 2.72 (m, 2H), 2.03 (s, 3H); 13 C NMR (100 MHz, CDCl3)δ 171.40, 169.97, 139.99, 128.51, 128.45,126.46, 52.62, 51.90, 36.06, 34.18, 34.05, 23.04; HRMS (LCMS-ESI)m / z Calcd. for C 14 H 19 NO3SNa [M+Na] + 304.0978, found: 304.0982. Example 25

[0100] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) was added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 34 μL of 4-allyl anisole (0.2 mmol, 1.0 equiv.), and 47 μL of thiobenzoic acid (0.4 mmol, 2.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was then separated by preparative thin-layer chromatography to obtain 49.1 mg of pure product, with a yield of 86%.

[0101] 1 H NMR (400 MHz, CDCl3)δ 8.02 – 7.96 (m, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.45 (t, J = 7.7 Hz, 2H), 7.13 (d, J = 8.6 Hz, 2H), 6.85 (d, J = 8.6 Hz, 2H), 3.79(s, 3H), 3.09 (t, J = 7.3 Hz, 2H), 2.76 – 2.67 (m, 2H), 2.04 – 1.94 (m, 2H); 13 C NMR (100 MHz, CDCl3)δ 192.05, 158.02, 137.30, 133.38, 133.32,129.49, 128.69, 127.30, 113.96, 55.36, 34.13, 31.47, 28.51; HRMS (LCMS-ESI)m / z Calcd. for C 17 H 18 O2SNa [M+Na] + 309.0920, found: 309.0928. Example 26

[0102] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) and 153 mg of 1-thio-β-D-glucose tetraacetate (0.4 mmol, 2.0 equiv.) were added. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 24 μL of styrene (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 82.4 mg of pure product, with a yield of 88%.

[0103] 1 H NMR (400 MHz, CDCl3)δ 7.29 (dd, J = 13.4, 6.0 Hz, 2H), 7.22 (dd, J =10.5, 7.5 Hz, 3H), 5.20 (t, J = 9.3 Hz, 1H), 5.06 (dt, J = 13.7, 9.7 Hz, 2H), 4.45 (d, J = 10.0 Hz, 1H), 4.24 (dd, J = 12.4, 4.9 Hz, 1H), 4.14 (dd, J = 12.3, 1.8Hz, 1H), 3.67 (ddd, J = 9.8, 4.7, 2.0 Hz, 1H), 3.02 – 2.86 (m, 4H), 2.03 (dd, J =14.4, 7.0 Hz, 12H); 13 C NMR (100 MHz, CDCl3)δ 170.72, 170.26, 169.49, 169.47, 140.12,128.63, 128.59, 126.60, 83.55, 76.00, 73.93, 69.91, 68.39, 62.24, 36.38,31.31, 20.82, 20.78, 20.69, 20.67; HRMS (LCMS-ESI)m / z Calcd. for C 22 H 28 O9SNa [M+Na] +491.1346, found: 491.1353. Example 27

[0104] To a 10 mL Schlenk reaction tube, add 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.), 23.2 mg of 1-ethynyl-4-methylbenzene (0.2 mmol, 1.0 equiv.), and 50 mg of 4-methylthiophenol (0.4 mmol, 2.0 equiv.), and then add 1.0 mL of ultradry acetonitrile under N2 conditions. The reaction mixture was stirred under blue light at room temperature for 24 h. After the reaction was complete, the mixture was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was then separated by preparative thin-layer chromatography to obtain 22.4 mg of pure product, with a yield of 47%.

[0105] 1 H NMR (400 MHz, CDCl3)δ 7.42 (d, J = 8.1 Hz, 1H), 7.35 (d, J = 8.2 Hz, 1H), 7.31 (d, J = 8.1 Hz, 1H), 7.21 (dt, J = 10.9, 5.5 Hz, 2H), 7.14 (d, J = 7.4Hz, 2H), 7.10 (d, J = 8.0 Hz, 1H), 6.79 (d, J = 15.4 Hz, 0.6H), 6.65 (d, J = 15.4Hz, 0.6H), 6.51 (d, J = 10.7 Hz, 0.4H), 6.39 (d, J = 10.7 Hz, 0.4H), 2.37 – 2.30(m, 6H); 13 C NMR (100 MHz, CDCl3)δ 137.46, 137.40, 137.18, 137.01, 134.03,133.92, 132.97, 131.65, 131.20, 130.56, 130.44, 130.04, 129.49, 129.13,128.80, 126.74, 126.01, 125.96, 123.04, 21.41, 21.33, 21.21; HRMS (LCMS-ESI)m / z Calcd. for C 16 H 17 S [M+H] + 241.1046, found: 241.1022. Example 28

[0106] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) was added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 46 μL of diallyl phthalate (0.2 mmol, 1.0 equiv.), and 18 μL of 1,2-ethylenedithiol (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 14 mg of pure product, with a yield of 21%.

[0107] 1 H NMR (400 MHz, CDCl3)δ 7.77 – 7.71 (m, 2H), 7.59 – 7.52 (m, 2H), 4.46 (t, J = 5.9 Hz, 4H), 2.75 (s, 4H), 2.71 – 2.64 (m, 4H), 2.04 (dq, J = 9.8, 6.1 Hz, 4H); 13 C NMR (100 MHz, CDCl3)δ 167.72, 132.24, 131.38, 129.23, 64.50,32.55, 29.49, 28.79; HRMS (LCMS-ESI)m / z Calcd. for C 16 H 20 O4S2Na [M+Na] + 363.0695, found: 363.0685. Example 29

[0108] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) was added. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 46 μL of diallyl phthalate (0.2 mmol, 1.0 equiv.), and 21 μL of 1,2-propanedithiol (0.2 mmol, 1.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 14.7 mg of pure product in 21% yield.

[0109] 1 H NMR (400 MHz, CDCl3)δ 7.74 (tt, J = 7.6, 3.2 Hz, 2H), 7.59 – 7.52 (m,2H), 4.53 – 4.36 (m, 4H), 2.96 – 2.82 (m, 2H), 2.77 – 2.60 (m, 4H), 2.58 –2.48 (m, 1H), 2.14 – 1.91 (m, 4H), 1.31 (d, J = 7.0 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 167.80, 167.65, 132.36, 132.11, 131.42,131.33, 129.26, 129.19, 64.65, 40.67, 39.83, 29.53, 29.34, 29.20, 28.27,20.31; HRMS (LCMS-ESI)m / z Calcd. for C 17 H 22 O4S2Na [M+Na] + 377.0852, found: 377.0851. Example 30

[0110] To a 10 mL Schlenk reaction tube, add 18.7 mg BINAP (0.03 mmol, 0.15 equiv.), 79 mg allyl-tetra-O-acetyl-β-D-glucopyranoside (0.2 mmol, 1.0 equiv.), and 73 mg N-acetyl-L-cysteine ​​methyl ester (0.4 mmol, 2.0 equiv.), and then add 1.0 mL of ultradry acetonitrile under N2 conditions. The reaction mixture was stirred under blue light at room temperature for 24 h. After the reaction was complete, the mixture was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was then separated by preparative thin-layer chromatography to obtain 77.9 mg of pure product, with a yield of 69%.

[0111] 1 H NMR (400 MHz, CDCl3)δ 6.35 (d, J = 7.4 Hz, 1H), 5.19 (t, J = 9.5 Hz, 1H), 5.07 (t, J = 9.7 Hz, 1H), 5.00 – 4.91 (m, 1H), 4.80 (dt, J = 7.5, 5.0 Hz, 1H), 4.49 (d, J = 8.0 Hz, 1H), 4.27 (dd, J = 12.3, 4.6 Hz, 1H), 4.14 (dd, J = 12.3, 2.1 Hz, 1H), 3.92 (dt, J = 9.9, 5.8 Hz, 1H), 3.76 (s, 3H), 3.69 (ddd, J = 9.9,4.4, 2.3 Hz, 1H), 3.59 (dt, J = 9.6, 6.2 Hz, 1H), 3.04 – 2.90 (m, 2H), 2.56 (t, J = 5.5 Hz, 2H), 2.10 – 1.97 (m, 15H), 1.91 – 1.74 (m, 2H); 13C NMR (100 MHz, CDCl3)δ 171.40, 170.82, 170.41, 169.99, 169.55,169.46, 100.98, 72.92, 71.97, 71.42, 68.49, 68.15, 62.02, 52.81, 52.13,34.23, 29.42, 29.15, 23.25, 20.88, 20.81, 20.74, 20.73; HRMS (LCMS-ESI)m / z Calcd. for C 23 H 35 NO 13 SNa [M+Na] + 588.1721, found: 588.1730. Example 31

[0112] To a 10 mL Schlenk reaction tube, add 18.7 mg BINAP (0.03 mmol, 0.15 equiv.), 79 mg allyl-tetra-O-acetyl-β-D-glucopyranoside (0.2 mmol, 1.0 equiv.), and 153 mg 1-thio-β-D-glucopyranoside (0.4 mmol, 2.0 equiv.), and then add 1.0 mL of ultradry acetonitrile under N2 conditions. The reaction mixture was stirred under blue light at room temperature for 24 h. After the reaction was complete, the mixture was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was then separated by preparative thin-layer chromatography to obtain 84.4 mg of pure product, with a yield of 56%.

[0113] 1 H NMR (400 MHz, CDCl3)δ 5.20 (dt, J = 19.0, 7.8 Hz, 2H), 5.05 (td, J =9.6, 4.7 Hz, 2H), 4.97 (dd, J = 19.5, 9.8 Hz, 2H), 4.51 – 4.42 (m, 2H), 4.28 –4.16 (m, 2H), 4.11 (d, J = 12.2 Hz, 2H), 3.95 – 3.85 (m, 1H), 3.69 (dd, J = 12.9, 6.2 Hz, 2H), 3.60 (dd, J= 14.7, 7.6 Hz, 1H), 2.79 – 2.58 (m, 2H), 2.08 – 1.96(m, 24H), 1.94 – 1.79 (m, 2H); 13 C NMR (100 MHz, CDCl3)δ 170.73, 170.66, 170.32, 170.23, 169.50,169.41, 100.96, 84.37, 75.93, 73.90, 72.84, 71.90, 71.37, 70.07, 68.49,68.42, 68.11, 62.25, 62.00, 30.05, 27.31, 20.81, 20.78, 20.67; HRMS (LCMS-ESI)m / z Calcd. for C 31 H 48 NO 19 S [M+NH4] + 770.2536, found: 770.2541. Example 32

[0114] To a 10 mL Schlenk reaction tube, add 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.), 64.5 mg of pent-4-en-1-yl 4-((1,1'-biphenyl)-4-yl)-4-oxobutyrate (0.2 mmol, 1.0 equiv.), and 153 mg of 1-thio-β-D-glucose tetraacetate (0.4 mmol, 2.0 equiv.), and then add 1.0 mL of ultradry acetonitrile under N2 conditions. The reaction mixture was stirred under blue light at room temperature for 24 h. After the reaction was complete, the mixture was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was then separated by preparative thin-layer chromatography to obtain 117 mg of pure product, with a yield of 85%.

[0115] 1 H NMR (400 MHz, CDCl3)δ 8.05 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 7.6 Hz, 2H), 7.46 (t, J = 7.5 Hz, 2H), 7.39 (t, J= 7.3 Hz, 1H), 5.21 (t, J = 9.4 Hz, 1H), 5.05 (dt, J = 19.5, 9.7 Hz, 2H), 4.48 (d, J = 10.0 Hz, 1H), 4.24 (dd, J = 12.4, 4.8 Hz, 1H), 4.11 (dt, J = 9.6, 4.3 Hz, 3H), 3.70 (ddd, J = 10.0, 4.7, 2.2 Hz, 1H), 3.34 (t, J = 6.6 Hz, 2H), 2.77 (t, J = 6.6 Hz, 2H), 2.74 – 2.59 (m, 2H), 2.06 (d, J = 7.5 Hz, 6H), 2.00 (d, J = 4.6 Hz, 6H), 1.69 – 1.57 (m, 4H), 1.45 (dd, J = 14.8, 7.0 Hz, 2H); 13 C NMR (100 MHz, CDCl3) δ 197.81, 173.05, 170.74, 170.28, 169.51, 169.50, 145.98, 139.92, 135.35, 129.06, 128.73, 128.35, 127.36, 83.63, 75.96, 73.97, 69.95, 68.39, 64.53, 62.23, 33.49, 29.82, 29.28, 28.37, 28.22, 25.17, 20.84, 20.82, 20.71, 20.67; HRMS (LCMS-ESI) m / z Calcd. for C 35 H 42 O 12 SNa [M+Na] + 709.2289, found: 709.2288. Example 33

[0116] To a 10 mL Schlenk reaction tube, 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) and 55 mg of N-(4-phenylthiazol-2-yl)hept-6-enamide (0.2 mmol, 1.0 equiv.) were added sequentially. Under N2 conditions, 1.0 mL of ultradry acetonitrile and 32 μL of thioacetic acid (0.4 mmol, 2.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 49.5 mg of pure product, with a yield of 71%.

[0117] 1 H NMR (400 MHz, CDCl3)δ 11.61 (s, 1H), 7.82 (d, J = 7.3 Hz, 2H), 7.42(t, J = 7.5 Hz, 2H), 7.34 (t, J = 7.3 Hz, 1H), 7.15 (s, 1H), 2.79 (t, J = 7.4 Hz,2H), 2.32 (s, 3H), 1.94 – 1.84 (m, 2H), 1.49 – 1.33 (m, 4H), 1.14 (dt, J =15.2, 7.5 Hz, 2H), 1.01 – 0.90 (m, 2H); 13 C NMR (100 MHz, CDCl3)δ 196.12, 171.66, 159.99, 149.55, 134.41,129.07, 128.45, 126.39, 108.00, 35.65, 30.76, 29.33, 29.06, 28.43, 28.35,24.53; HRMS (LCMS-ESI)m / z Calcd. for C 18 H 23 N₂O₂S₂[M+H] + 363.1196, found: 363.1202. Example 34

[0118] Method 1: 18.7 mg of BINAP (0.03 mmol, 0.15 equiv.) was added to a 10 mL Schlenk reaction tube. Under N2 conditions, 1.0 mL of ultradry acetonitrile, 38 μL of 9-bromo-1-nonene (0.2 mmol, 1.0 equiv.), and 60 μL of pentafluoropentanethiol (0.4 mmol, 2.0 equiv.) were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was complete, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. Preparative thin-layer chromatography was used to separate the product, yielding 55.9 mg of pure product (70% yield).

[0119] Method 2: 1 mg (0.002 mmol, 0.01 equiv.) of phosphine salt catalyst (Formula (6)) was added to a 10 mL Schlenk reaction tube. Under N2 conditions, 1.0 mL of ultra-dry acetonitrile, 38 μL (0.2 mmol, 1.0 equiv.) of 9-bromo-1-nonene, and 60 μL (0.4 mmol, 2.0 equiv.) of pentafluoropentanethiol were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was completed, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 76.2 mg of pure product, with a yield of 95%.

[0120] 1 H NMR (400 MHz, CDCl3)δ 3.40 (t, J = 6.9 Hz, 2H), 2.58 (t, J = 7.0 Hz,2H), 2.54 – 2.45 (m, 2H), 2.16 (ddd, J = 17.9, 13.1, 6.2 Hz, 2H), 1.92 – 1.79(m, 4H), 1.62 – 1.51 (m, 2H), 1.45 – 1.33 (m, 4H), 1.30 (s, 6H); HRMS (LCMS-ESI)m / z Calcd. for C 14 H 24 BrF5SK [M+K] + 437.0334, found: 437.0351. Example 35

[0121] 14.2 mg (0.03 mmol, 0.15 equiv.) of phosphine salt catalyst (formula (6)) was added to a 10 mL Schlenk reaction tube. Under N2 conditions, 1.0 mL of hydrogen sulfide acetonitrile solution, 33 μL (0.2 mmol, 1.0 equiv.) of 4-allyl anisole, and 20 μL (0.5 mmol, 2.5 equiv.) of formic acid were added sequentially. The reaction was stirred under blue light at room temperature for 24 h. After the reaction was completed, the product was diluted with ethyl acetate, filtered, and the solvent was removed by vacuum distillation. The product was separated by preparative thin-layer chromatography to obtain 20.9 mg of pure product, with a yield of 63%.

[0122] 1 H NMR (400 MHz, CDCl3)δ 7.10 (d, J = 8.4 Hz, 4H), 6.83 (d, J = 8.4 Hz, 4H), 3.79 (s, 6H), 2.66 (t, J = 7.5 Hz, 4H), 2.51 (t, J = 7.3 Hz, 4H), 1.92 –1.80 (m, 4H); 13 C NMR (100 MHz, CDCl3)δ 157.95, 133.76, 129.48, 113.91, 55.38,34.01, 31.49, 31.45; HRMS (LCMS-ESI)m / z Calcd. for C 20 H 27 O2S [M+H] + 331.1726, found: 331.1724. The raw materials used in this invention are inexpensive and readily available, the reaction operation is simple and practical, the conditions are mild, and it has good universality and biocompatibility. It solves the technical bottleneck problems of harsh conditions and lack of biocompatibility faced by existing technologies, and is a breakthrough in existing synthesis technologies with high application value.

[0123] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of this invention.

Claims

1. A photocatalytic synthesis method for dialkyl sulfide compounds, characterized in that, include: Using unsaturated hydrocarbons and sulfur sources as raw materials, and phosphine catalyst as photocatalyst, the reaction is carried out in a solvent and under inert gas protection, and irradiated with blue light to obtain dialkyl sulfide compounds.

2. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 1, characterized in that, The unsaturated hydrocarbon is an olefin or an alkyne.

3. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 2, characterized in that, The olefin has the structural formula shown in formula (1) or formula (2), and the alkyne has the structural formula shown in formula (3): R1, R2 and R3 are each independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, ester group, or R2 and R3 are connected to form a cycloalkyl or substituted cycloalkyl; R4 is selected from oxygen, alkyl, substituted alkyl, substituted amino group, phthalic acid group; R5 and R6 are each independently selected from hydrogen, alkyl, aryl, substituted aryl.

4. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 2, characterized in that, The olefin is 1-allyl-2-methoxybenzene, allyl phenyl carbonate, 1-allylbenzotriazole, vinyl benzoate, vinyl acetate, allyl ether, 9-bromo-1-nonene, 4-allyl anisole, styrene, diallyl phthalate, but-3-en-1-yl(4-chlorophenyl) sulfide, diethyl allyl malonate, diethyl diallyl malonate, 3-methylbut-3-enyl benzoate, 3-cyclopentene-1- Dimethyl 1-dicarboxylate, N,N-diallylcarbamate tert-butyl ester, N,N-diallyl-4-methylbenzenesulfonamide, N,N-diallyl-3-bromo-4-chlorobenzenesulfonamide, allyl-tetra-O-acetyl-β-D-glucopyranoside, N-(4-phenylthiazol-2-yl)hept-6-enamide, 3-allyl-3-toluenesulfonylhex-5-en-2-one, pent-4-en-1-yl 4-((1, 1'-Biphenyl)-4-yl)-4-oxobutyrate, pent-4-en-1-yl 2-(4-(2-(4-chlorobenzoamido)ethyl)phenoxy)-2-methylpropionate, pent-4-en-1-yl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate, 3-methylbut-3-en-1-yl 2-(4-isobutylphenyl)propionate, 3-methylbut-3-yl ester One of the following: 1-en-1-yl 2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazolyl-5-carboxylic acid ester, (1r,4R)-N-((R)-1-(diallylamino)-1-oxo-3-phenylpropan-2-yl)-4-isopropylcyclohexane-1-carboxamide, and 4-chloro-N-(4-((1-(diallylamino)-2-methyl-1-oxopropan-2-yl)oxy)phenethyl)benzamide; The alkyne is 1-ethynyl-4-methylbenzene.

5. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 1, characterized in that, The sulfur source is sodium sulfide, hydrogen sulfide, thiols, or dithiols; when the sulfur source is sodium sulfide or hydrogen sulfide, the method further includes using an organic acid as an additive.

6. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 5, characterized in that, The structural formula of the thiol is shown in formula (4), and the structural formula of the dithiol is shown in formula (5): R7 is selected from alkyl, substituted alkyl, aryl, substituted aryl, and glycosyl; R8 is an alkyl group.

7. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 5, characterized in that, The thiol is benzyl thiol, 4-methylbenzyl thiophenol, N-acetyl-L-cysteine ​​methyl ester, thiobenzoic acid, 1-thio-β-D-glucose tetraacetate, 1-thio-β-D-glucose tetraacetate, thioacetic acid, or pentafluoropentanethiol; the dithiol is 1,2-ethanedithiol or 1,2-propanedithiol.

8. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 5, characterized in that, When the sulfur source is sodium sulfide, the phosphine catalyst is 1,1'-binaphthyl-2,2'-bisdiphenylphosphine; when the sulfur source is hydrogen sulfide, thiol or dithiol, the phosphine catalyst is 1,1'-binaphthyl-2,2'-bisdiphenylphosphine or a phosphine salt of formula (6); Where X is Cl — or Br — .

9. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 5, characterized in that, The organic acid is formic acid, acetic acid, trifluoroacetic acid, or trifluoromethanesulfonic acid.

10. The photocatalytic synthesis method for dialkyl sulfide compounds according to claim 1, characterized in that, The solvent is acetonitrile, acetone, diethyl ether, dichloromethane, ethanol, PBS buffer, or water.

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