A method for synthesizing thioesters based on unsaturated hydrocarbons

Abstract

The application discloses a method for synthesizing thiocarboxylic acid ester based on unsaturated hydrocarbon; the method uses substituted unsaturated hydrocarbon and thiocarboxylic acid ester as raw materials, and under the synergistic catalysis of a transition metal catalyst and visible light, the reaction is carried out in an organic solvent at room temperature for 12-24 hours. The application can realize the transhydrogenation carbonyl reaction of unsaturated hydrocarbon and thiocarboxylic acid ester at room temperature. The reaction condition is mild, the regioselectivity is high, and the atomic economy is 100%. The raw materials, catalysts and additives used in the reaction are cheap and easy to obtain, the synthesis process is simple, and the synthesis cost is greatly reduced; meanwhile, the direct use of toxic gas CO and foul-smelling sulfenol is avoided in the reaction, so that the reaction condition is safer and greener, and the reaction is easy to industrialize.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and more specifically, to a method for synthesizing thiocarboxylic acid esters based on unsaturated hydrocarbons. Background Technology

[0002] Thiocarboxylic esters, as an important branch of sulfur-containing compounds, have attracted widespread attention due to their unique chemical and biological activities. Many active skeletons possess this substructure, and it has numerous applications in organic synthesis. This structure is found in coenzyme A, a common enzyme in organisms, and is ubiquitous in metabolic activities, playing a crucial role in the metabolism of living organisms. Polyketide synthases and polypeptide synthases in organisms utilize thiocarboxylic esters in fatty acid and amino acid molecules as important reaction sites to synthesize and assemble biologically active polyketides and polypeptides. Therefore, the efficient synthesis of thiocarboxylic esters is particularly important.

[0003] Traditional methods for synthesizing thioesters involve direct nucleophilic addition-elimination reactions of thiols or thiophenols with appropriate acyl chlorides or acid anhydrides. Furthermore, these substances can be synthesized by condensation of corresponding carboxylic acids with thiols or thiophenols under different catalytic conditions to yield the corresponding thiocarboxylic acid esters. Building upon this foundation, chemical researchers have expanded the versatility of these reaction substrates by developing highly efficient catalysts, from highly reactive acyl chlorides and acid anhydrides to carboxylic acids, and then to less reactive esters and amides. Due to the high efficiency of the catalysts, thiocarboxylic acid esters can still be obtained in high yields. These methods are relatively classic synthetic approaches, all using carboxylic acid derivatives as reaction precursors; additionally, they require thiols with a foul odor. While the direct hydrothiocarbonylation of alkenes or alkynes provides a 100% atom-economical route for the synthesis of these substances... Although the above-mentioned reactions for synthesizing thioesters provide an important pathway for the synthesis and transformation of these substances, they still face some challenges. For example, the above reactions require (1) high temperature and high pressure; (2) equivalent amounts of thiols or thiophenols, which have an unpleasant odor and are environmentally unfriendly; and (3) the carbonyl source used in the reaction comes from toxic CO gas, which has a low safety factor and requires a high-quality operating environment. Therefore, developing more efficient, simple, green, and environmentally friendly synthetic routes remains a hot topic for chemists. Summary of the Invention

[0004] The purpose of this invention is to provide a method for synthesizing thiocarboxylic acid esters based on unsaturated hydrocarbons, which overcomes the limitations of the existing methods for synthesizing thiocarboxylic acid esters.

[0005] To solve the above-mentioned technical problems, the present invention provides a method for synthesizing thiocarboxylic acid esters based on unsaturated hydrocarbons. The method includes: mixing unsaturated hydrocarbons, thiocarboxylic acid esters (I), metal catalysts, ligands and organic solvents, and reacting them under visible light to synthesize thiocarboxylic acid esters (II).

[0006]

[0007] Wherein, R is selected from various substituted aryl and naphthalene groups;

[0008] R 1 R 2 Selected from various substituted aryl or alkyl carbon chains.

[0009] Preferably, R 1 R 2 It is an alkyl-substituted hydrocarbon, containing one or more of the following functional groups: halogen, aldehyde, ester, amino, and ketone.

[0010] Preferably, the R group is an aromatic hydrocarbon substituted with an electron-withdrawing group or an aromatic hydrocarbon substituted with an electron-donating group;

[0011] Preferably, the unsaturated hydrocarbon is an olefin or an alkyne.

[0012] Preferably, the reaction conditions include conducting the reaction synthesis at room temperature.

[0013] Preferably, the metal catalyst is selected from palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium chloride diacetonitrile, tris(dibenzylideneacetone)dipalladium, tetra(triphenylphosphine)palladium, bisbenzonitrile palladium chloride, and cyclooctadiene palladium bromide.

[0014] Preferably, the ligand is selected from 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene and bis(2-diphenylphosphine) ether.

[0015] Preferably, the organic solvent is selected from one of dichloromethane, chloroform, toluene, tetrahydrofuran, ethyl acetate, N,N-diethylamide, anisole, and iodoethane;

[0016] Preferably, the concentration of the organic solvent is 0.1-1M.

[0017] Preferably, the method includes: mixing a metal catalyst and a ligand and then converting the mixture under nitrogen, followed by sequentially adding an organic solvent, an unsaturated hydrocarbon, and a thiocarboxylic acid ester (I); reacting the mixture at room temperature under blue light irradiation for 12-24 hours; removing dichloromethane by rotary evaporation after the reaction to obtain a crude product; and obtaining a thiocarboxylic acid ester (II) by column chromatography.

[0018] This invention provides a method for synthesizing thiocarboxylic acid esters based on unsaturated hydrocarbons, wherein the thiocarboxylic acid esters are prepared by the method described above.

[0019] The present invention also provides the applicability of the above-described thiocarboxylic acid esters in the modification of bioactive molecules and natural products.

[0020] This invention provides a method for synthesizing thiocarboxylic acid esters based on unsaturated hydrocarbons. This synthetic method avoids the use of odorous thiols or toxic CO gas, offering a novel route for the efficient synthesis of thioesters. Using thiocarbamate as a thioformyl source, the thiocarbamate is activated under transition metal catalysis, introducing both the sulfur and carbonyl sources into the unsaturated hydrocarbon. This reaction strategy is carried out at room temperature, uses readily available and simple reactants, is easy to process and purify, and yields high results, providing an excellent supplementary method to existing thioester synthesis methods.

[0021] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0022] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0023] Figure 1 This is the hydrogen spectrum of the thiocarboxylic acid ester obtained in Example 36;

[0024] Figure 2 This is the carbon spectrum of the thiocarboxylic acid ester prepared in Example 36. Detailed Implementation

[0025] The specific embodiments of the present invention will be described in detail below.

[0026] Example 1: Preparation of Thioester

[0027]

[0028] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, and then dichloromethane (1 mL), iodoethane (3 μL), styrene (20.8 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 47.1 mg of a colorless oil, with a yield of 92% (yield calculated based on olefins). NMR characterization data are as follows: 1H NMR (600MHz, CDCl3) δ7.23-7.30(m,4H),7.19-7.20(m,5H),3.00(t,J=7.2Hz,2H),2.94(t,J=7.2Hz,2H),2.36(s,3H); 13 C NMR (151MHz, CDCl3) δ197.2,140.1,139.8,134.6,130.1,128.7,128.5,126.5,124.4,45.2,31.6,21.4.

[0029] Example 2: Preparation of thioesters

[0030]

[0031] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, and then dichloromethane (1 mL), iodoethane (3 μL), p-methylstyrene (23.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 46.4 mg of a white solid, with a yield of 86% (yield calculated based on olefins). NMR characterization data are as follows: 1 H NMR(600MHz, CDCl3)δ7.25(d,J=7.8Hz,2H),7.19(d,J=7.8Hz,2H),7.08-7.09( m,4H),2.96(t,J=7.2Hz,2H),2.92(t,J=7.2Hz,2H),2.36(s,3H),2.31(s,3H); 13 C NMR (151MHz, CDCl3) δ197.3,139.7,137.1,136.0,134.6,130.1,129.4,128.4,124.4,45.3,31.2,21.4,21.1.

[0032] Example 3: Preparation of Thioester

[0033]

[0034] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 2-methylstyrene (23.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 51.8 mg of a white solid, with a yield of 96% (yield calculated based on olefins). NMR characterization data were as follows: 1 H NMR(600MHz, CDCl3)δ7.26(d,J=7.8Hz,2H),7.20(d,J=7.8Hz,2H),7.12-7.13( m,4H),3.00(t,J=7.2Hz,2H),2.89(t,J=7.2Hz,2H),2.36(s,3H),2.32(s,3H); 13 C NMR (151MHz, CDCl3) δ197.3,139.8,138.3,136.1,134.6,130.5,130.1,128.9,126.7,126.3,124.4,43.9,29.0,21.4,19.3.

[0035] Example 4: Preparation of Thioesters

[0036]

[0037] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-methoxystyrene (26.8 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 47.6 mg of a white solid, with a yield of 83% (yield calculated based on olefins). NMR characterization data were as follows: 1 H NMR (600MHz, CDCl3) δ7.25(d,J=7.8Hz,2H),7.20(d,J=7.8Hz,2H),7.11(d,J=7 .8Hz,2H),6.83(d,J=7.8Hz,2H),3.79(s,3H),2.89-2.96(m,4H),2.37(s,3H);13 C NMR (151MHz, CDCl3) δ197.3,158.3,139.8,134.6,132.2,130.1,129.5,124.4,114.1,55.4,45.5,30.8,21.5.

[0038] Example 5: Preparation of Thioesters

[0039]

[0040] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-fluorostyrene (24.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 47.6 mg of a white solid, with a yield of 83% (yield calculated based on olefins). NMR characterization data were as follows: 1 H NMR(600MHz, CDCl3)δ7.24(d,J=8.4Hz,2H),7.20(d,J=7.8Hz,2H),7.14-7.16(m, 2H),6.96-6.99(m,2H),2.97(t,J=7.2Hz,2H),2.92(t,J=6.6Hz,2H),2.37(s,3H); 13 C NMR(151MHz,CDCl3)δ197.1,160.9(d,J C-F =244.6Hz), 139.9, 135.7((d,J) C-F =3.0Hz),134.5,130.2,129.9(d,J C-F =7.6Hz), 124.2, 115.4 (d, J) C-F =21.1Hz), 45.2, 30.7, 21.4; 19 F NMR (376MHz, CDCl3) δ-116.8.

[0041] Example 6: Preparation of Thioesters

[0042]

[0043] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-chlorostyrene (27.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 49.2 mg of a white solid, with a yield of 85% (yield calculated based on olefins). NMR characterization data were as follows: 1 H NMR (600MHz, CDCl3) δ7.24-7.26(m,4H),7.20(d,J=8.4Hz,2H),7.12(d,J=7.8Hz,2H),2.97(t,J=7.2Hz,2H),2.92(t,J=7.8Hz,2H),2.37(s,3H); 13 C NMR (151MHz, CDCl3) δ197.0,139.9,138.6,134.5,132.3,130.2,129.9,128.8,124.2,44.9,30.8,21.4.

[0044] Example 7: Preparation of Thioester

[0045]

[0046] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-bromostyrene (36.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 59.2 mg of a white solid, with a yield of 89% (yield calculated based on olefins). NMR characterization data were as follows: 1 H NMR (600MHz, CDCl3) δ7.40(d,J=7.8Hz,2H),7.24(d,J=6.6Hz,2H),7.20(d,J=7.8Hz,2H),7.07(d,J=7.8Hz,2H),2.92-2.95(m,4H),2.37(s,3H); 13C NMR (151MHz, CDCl3) δ197.0,139.9,139.1,134.5,131.7,130.3,130.2,124.2,120.4,44.8,30.9,21.4.

[0047] Example 8: Preparation of Thioesters

[0048]

[0049] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, and then dichloromethane (1 mL), iodoethane (3 μL), methyl 4-vinylbenzoate (32.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 54.8 mg of a white solid, with a yield of 87% (yield calculated based on olefins). NMR characterization data were as follows: 1 H NMR (600MHz, CDCl3) δ7.96 (d, J = 8.4Hz, 2H), 7.21-7.28 (m, 6H), 3.91 (s, 3H), 3.06 (t, J = 7.2Hz, 2H), 2.97 (t, J = 7.8Hz, 2H), 2.37 (s, 3H); 13 CNMR (151MHz, CDCl3) δ196.9,167.1,145.5,139.9,134.6,130.2,130.0,128.6,124.1,52.2,44.5,31.4,21.5.

[0050] Example 9: Preparation of Thioesters

[0051]

[0052] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-cyanostylstyrene (25.8 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 47.3 mg of a white solid, with a yield of 84% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.58 (d, J = 8.4Hz, 2H), 7.30 (d, J = 7.8Hz, 2H), 7.21-7.25 (m, 4H), 3.06 (t, J = 7.2Hz, 2H), 2.97 (t, J = 7.2Hz, 2H), 2.37 (s, 3H); 13 C NMR (151MHz, CDCl3) δ196.6,145.7,140.1,134.5,132.5,130.2,129.4,123.9,118.9,110.6,44.1,31.4,21.4.

[0053] Example 10: Preparation of Thioesters

[0054]

[0055] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-vinylbenzaldehyde (26.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 49.6 mg of a white solid, with a yield of 87% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ9.98 (s, 1H), 7.81 (d, J = 7.8Hz, 2H), 7.36 (d, J = 7.8Hz, 2H), 7.24 (d, J = 8 .4Hz,2H),7.20(d,J=8.4Hz,2H),3.08(t,J=7.2Hz,2H),2.98(t,J=7.2Hz,2H),2.36(s,3H);13 C NMR (151MHz, CDCl3) δ196.7,191.9,147.3,139.9,135.1,134.5,130.2,130.2,129.2,124.0,44.3,31.5,21.4.

[0056] Example 11: Preparation of Thioester

[0057]

[0058] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), 4-nitrostyrene (29.8 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product, which was then directly analyzed by column chromatography to give 46.9 mg of a white solid, with a yield of 78% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ8.15(d,J=8.4Hz,2H),7.36(d,J=8.4Hz,2H),7.21-7.25(m,4H),3.11(t,J=7.8Hz,2H),3.00(t,J=7.8Hz,2H),2.37(s,3H); 13 C NMR (151MHz, CDCl3) δ196.6,147.8,146.9,140.1,134.5,130.2,129.5,123.9,123.8,44.1,31.1,21.4.

[0059] Example 12: Preparation of thioesters

[0060]

[0061] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), α-naphthylethylene (30.8 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 45.1 mg of a colorless oil, with a yield of 74% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ8.00(d,J=8.4Hz,1H),7.85(d,J=7.8Hz,1H),7.72(d,J=7.8Hz,1H),7.46-7.53(m,2H),7.33-7 .40(m,2H),7.26(d,J=7.8Hz,2H),7.19(d,J=7.8Hz,2H),3.47(t,J=7.8Hz,2H),3.06(t,J=8.4Hz,2H),2.36(s,3H); 13 C NMR (151MHz, CDCl3) δ197.4,139.8,136.2,134.6,134.1,131.7,130.2,129.1,127.4,126.4,126.3,125.8,125.7,124.3,123.5,44.4,28.8,21.4.

[0062] Example 13: Preparation of Thioesters

[0063]

[0064] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), α-vinylthiophene (22.0 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product, which was then directly analyzed by column chromatography to give 36.6 mg of a white solid, with a yield of 70% (yield calculated based on olefins). NMR characterization data... 1H NMR (600MHz, CDCl3) δ7.27(d,J=7.8Hz,2H),7.21(d,J=7.8Hz,2H),7.13(d,J=5.4Hz,1H),6. 92(t,J=4.2Hz,1H),6.83(s,1H),3.22(t,J=7.2Hz,2H),3.00(t,J=7.8Hz,2H),2.37(s,3H); 13 C NMR (151MHz, CDCl3) δ196.7,142.6,139.9,134.6,130.2,127.0,125.1,124.2,123.8,45.3,25.7,21.5.

[0065] Example 14: Preparation of Thioesters

[0066]

[0067] (1,5-Cyclooctadiene)palladium dibromide (3.7 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (1 mL), iodoethane (3 μL), α-methylstyrene (23.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 24 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 40.7 mg of a colorless oil, with a yield of 75% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.30 (t, J = 7.8Hz, 2H), 7.18-7.24 (m, 7H), 3.33-3.39 (m, 1H), 2.91 (dd ,J=14.4Hz,6.6Hz,1H),2.93(dd,J=14.4Hz,7.8Hz,1H),2.35(s,3H),1.34(d,J=6.6Hz,3H); 13 C NMR (151MHz, CDCl3) δ196.8,145.4,139.7,134.5,130.1,128.7,127.0,126.7,124.5,51.9,37.2,21.5,21.4.

[0068] Example 15: Preparation of Thioesters

[0069]

[0070] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was converted three times under nitrogen atmosphere, and then dichloromethane (2 mL), iodoethane (3 μL), 4-methoxyphenylpropene (29.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 55.8 mg of a colorless oil, with a yield of 93% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.26(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),7.09(d,J=8.4Hz,2H),6. 82(d,J=8.4Hz,2H),3.78(s,3H),2.60-2.66(m,4H),2.36(s,3H),1.99(quint,J=7.6Hz,2H); 13 C NMR (101MHz, CDCl3) δ198.0,158.1,139.7,134.6,133.3,130.1,129.6,124.4,114.0,55.4,42.9,34.1,27.4,21.5.

[0071] Example 16: Preparation of Thioesters

[0072]

[0073] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), styrene (23.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 48.6 mg of a colorless oil, with a yield of 90% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.27-7.31(m,4H),7.18-7.22(m,5H),2.64-2.70(m,4H),2.37(s,3H),2.03(quint,J=7.6Hz,2H); 13C NMR (101MHz, CDCl3) δ197.9,141.3,139.7,134.6,130.1,128.6,128.5 126.2,124.3,42.9,35.0,27.2,21.5.

[0074] Example 17: Preparation of Thioesters

[0075]

[0076] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 1-hexene (16.8 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 32.9 mg of a colorless oil, with a yield of 70% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.27(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),2.63(t,J=7.2 Hz,2H),2.36(s,3H),1.64-1.73(m,2H),1.29-1.36(m,6H),0.89(t,J=6.8Hz,3H); 13 C NMR (101MHz, CDCl3) δ198.2,139.6,134.6,130.1,124.5,43.7,31.6,28.7,25.7,22.6,21.4,14.2.

[0077] Example 18: Preparation of Thioesters

[0078]

[0079] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was converted three times under nitrogen atmosphere, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 10-undecenal (33.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 57.2 mg of a green solid, with a yield of 89% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ9.76 (s, 1H), 7.27 (d, J = 8.0Hz, 2H), 7.20 (d, J = 8.0Hz, 2H), 2.6 3(t,J=7.2Hz,2H),2.40-2.44(m,2H),2.37(s,3H),1.58-1.73(m,4H),1.28(m,12H); 13 C NMR (101MHz, CDCl3) δ203.2,198.3,139.7,134.6,130.1,124.5,44.0,43.7,29.4,29.4,29.3,29.2,29.0,25.7,22.2,21.5.

[0080] Example 19: Preparation of Thioesters

[0081]

[0082] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The tube was converted three times under nitrogen atmosphere, and then dichloromethane (2 mL), iodoethane (3 μL), methyl 10-undecenoate (39.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product, which was directly analyzed by column chromatography to give 52.5 mg of a white solid, with a yield of 75% (yield calculated based on olefins). NMR characterization data... 1H NMR (400MHz, CDCl3) δ7.27(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),3.67(s,3H),2.63(t, J=7.6Hz,2H),2.37(s,3H),2.30(d,J=7.6Hz,2H),1.60-1.71(m,4H),1.28-1.34(m,12H); 13 C NMR (101MHz, CDCl3) δ198.3,174.5,139.7,134.6,130.1,124.5,51.6,43.7,34.2,29.5,29.4,29.3,29.2,29.0,25.7,25.0,21.5.

[0083] Example 20: Preparation of Thioesters

[0084]

[0085] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 5-hexenylphenyl ether (35.2 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 59.7 mg of a colorless oil, with a yield of 91% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.25-7.29(m,4H),7.19(d,J=6.4Hz,2H),6.87-6.94(m,3H),3.93(t ,J=6.4Hz,2H),2.64(t,J=7.6Hz,2H),2.36(s,3H),1.70-1.81(m,4H),1.42-1.51(m,4H); 13 C NMR (101MHz, CDCl3) δ198.1,159.1,139.7,134.5,130.1,129.5,124.4,120.6,114.5,67.7,43.5,29.1,28.8,25.9,25.6,21.4.

[0086] Example 21: Preparation of Thioester

[0087]

[0088] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The tube was purged three times under nitrogen, and then dichloromethane (2 mL), iodoethane (3 μL), 5-hexen-1-ol (20.0 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 43.1 mg of a red oil, with a yield of 86% (yield calculated based on olefins). NMR characterization data... 1 H NMR (500MHz, CDCl3) δ7.27(d,J=8.0Hz,2H),7.21(d,J=8.0Hz,2H),3.63(t,J=6.5Hz,2H),2 .64(t,J=7.5Hz,2H),2.37(s,3H),1.69-1.75(m,3H),1.54-1.60(m,2H),1.37-1.40(m,4H); 13 C NMR (101MHz, CDCl3) δ198.2,139.7,134.6,130.1,124.4,62.9,43.6,32.6,28.8,25.6,25.5,21.4.

[0089] Example 22: Preparation of thioesters

[0090]

[0091] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 6-chloro-1-hexene (23.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 49.7 mg of a colorless oil, with a yield of 92% (yield calculated based on olefins). NMR characterization data... 1H NMR (400MHz, CDCl3) δ7.27(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),3.52(t,J=6.4 Hz,2H),2.64(t,J=7.2Hz,2H),2.37(s,3H),1.68-1.80(m,4H),1.35-1.49(m,4H); 13 C NMR (101MHz, CDCl3) δ198.0,139.7,134.5,130.1,124.3,45.1,43.4,32.4,28.2,26.6,25.4,21.4.

[0092] Example 23: Preparation of Thioesters

[0093]

[0094] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 6-bromo-1-hexene (32.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 60.7 mg of a colorless oil, with a yield of 96% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.27(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),3.39(t,J=6.8Hz,2H),2 .64(t,J=7.6Hz,2H),2.37(s,3H),1.82-1.89(m,2H),1.67-1.75(m,2H),1.34-1.49(m,4H); 13 C NMR (101MHz, CDCl3) δ198.0,139.7,134.5,130.1,124.3,43.4,33.9,32.5,28.1,27.8,25.4,21.4.

[0095] Example 24: Preparation of Thioesters

[0096]

[0097] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, and then dichloromethane (2 mL), iodoethane (3 μL), 5-iodo-1-pentene (39.2 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg) were added sequentially. The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 49.5 mg of a colorless oil, with a yield of 71% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.28(d,J=7.8Hz,2H),7.21(d,J=7.8Hz,2H),3.18(t,J=7.2Hz,2H),2 .66(t,J=7.2Hz,2H),2.37(s,3H),1.82-1.87(m,2H),1.70-1.75(m,2H),1.45-1.50(m,2H); 13 C NMR (151MHz, CDCl3) δ197.8,139.8,134.6,130.1,124.4,43.4,33.2,29.9,24.6,21.5,6.4.

[0098] Example 25: Preparation of Thioesters

[0099]

[0100] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), cyclohexene (16.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 29.4 mg of a colorless oil, with a yield of 63% (yield calculated based on olefins). NMR characterization data... 1H NMR (400MHz, CDCl3) δ7.27(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),2.56-2.63(m,1H),2.37(s,3H ),1.97-2.01(m,2H),1.79-1.83(m,2H),1.64-1.69(m,1H),1.46-1.56(m,2H),1.20-1.35(m,3H); 13 C NMR (101MHz, CDCl3) δ201.5,139.5,134.7,130.1,124.4,52.5,29.7,25.7,25.6,21.5.

[0101] Example 26: Preparation of Thioesters

[0102]

[0103] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 1-octene (22.4 mg), and S-(4-tert-butylphenyl)thiocarbamate (58.2 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 55.2 mg of a colorless oil, with a yield of 90% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.34(d,J=8.4Hz,2H),7.24(d,J=8.4Hz,2H),2.57(t,J=7.6Hz,2H),1.57-1.67(m,2H),1.20-1.25(m,19H),0.81(t,J=6.4Hz,3H); 13 C NMR (101MHz, CDCl3) δ198.2,152.6,134.2,126.4,124.6,43.8,34.9,31.9,31.3,29.3,29.2,29.1,25.8,22.8,14.2.

[0104] Example 27: Preparation of Thioester

[0105]

[0106] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 1-octene (22.4 mg), and S-(4-fluorophenyl)thiocarbamate (46.8 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 44.8 mg of a colorless oil, with a yield of 84% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.35-7.39(m,2H),7.07-7.13(m,2H),2.64(t,J=7.6Hz,2H),1.67-1.74(m,2H),1.28-1.37(m,10H),0.88(t,J=6.8Hz,3H); 13 C NMR(101MHz,CDCl3)δ197.7,162.3(d,J C-F =251.5Hz), 136.6(d,J) C-F =8.1Hz), 123.4(d,J C-F =4.0Hz), 116.4(d,J C-F =22.2Hz),43.8,31.9,29.3,29.2,29.1,25.7,22.8,14.2; 19 F NMR (376MHz, CDCl3) δ-111.4.

[0107] Example 28: Preparation of Thioesters

[0108]

[0109] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 1-octene (22.4 mg), and S-(4-chlorophenyl)thiocarbamate (51.3 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 38.2 mg of a colorless oil, with a yield of 67% (yield calculated based on olefins). NMR characterization data... 1H NMR (400MHz, CDCl3) δ7.37(d,J=7.6Hz,2H),7.32(d,J=8.8Hz,2H),2.65(t,J=7.2Hz,2H),1.67-1.74(m,2H),1.28-1.35(m,10H),0.88(t,J=6.4Hz,3H); 13 C NMR (101MHz, CDCl3) δ197.2,135.8,129.5,126.5,43.9,31.9,29.3,29.2,29.1,25.7,22.8,14.2.

[0110] Example 29: Preparation of Thioester

[0111]

[0112] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 1-octene (22.4 mg), and S-(4-bromophenyl)thiocarbamate (64.8 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 64.9 mg of a colorless oil, with a yield of 99% (yield calculated based on olefins). NMR characterization data... 1 H NMR (400MHz, CDCl3) δ7.52(d,J=8.4Hz,2H),7.25(d,J=8.4Hz,2H),2.65(t,J=7.6Hz,2H),1.66-1.74(m,2H),1.27-1.35(m,10H),0.88(t,J=6.0Hz,3H); 13 C NMR (101MHz, CDCl3) δ197.1,136.0,132.5,127.1,124.1,43.9,31.9,29.3,29.2,29.1,25.7,22.8,14.2.

[0113] Example 30: Preparation of Thioesters

[0114]

[0115] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), 1-octene (22.4 mg), and S-(2-naphthyl)thiocarbamate (56.4 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 20.6 mg of a colorless oil, with a yield of 34% (yield calculated based on olefins). NMR characterization data... 1 H NMR(600MHz, CDCl3)δ7.93(s,1H),7.79-7.85(m,3H),7.43-7.51(m,3H),2.67( t,J=7.8Hz,2H),1.70-7.75(m,2H),1.29-1.37(m,10H),0.88(t,J=6.0Hz,3H); 13 C NMR (125MHz, CDCl3) δ197.8,134.4,133.7,133.4,131.1,128.8,128.1,12 7.9,127.2,126.6,125.5,43.9,31.9,29.3,29.2,29.1,25.8,22.8,14.2.

[0116] Example 31: Preparation of Thioester

[0117]

[0118] Tetraphenylphosphine palladium (11.6 mg) and bis(2-diphenylphosphine) ether (6.5 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), styrene (22.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 38.2 mg of a colorless oil, with a yield of 75% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.34-7.35(m,4H),7.28-7.30(m,1H),7.21(d,J=7.8Hz,2H) ,7.16(d,J=8.4Hz,2H),3.97(q,J=6.6Hz,1H),2.34(s,3H),1.56(d,J=7.2Hz,3H); 13C NMR (151MHz, CDCl3) δ199.5,139.8,139.6,134.5,130.0,128.9,128.2,127.7,124.6,54.1,21.4,18.8.

[0119] Example 32: Preparation of Thioester

[0120]

[0121] Tetraphenylphosphine palladium (11.6 mg) and bis(2-diphenylphosphine) ether (6.5 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), 4-methylstyrene (23.6 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 41.7 mg of a colorless oil, with a yield of 77% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.21-7.24(m,4H),7.16-7.17(m,4H),3.93(q,J=7.2Hz,1H),2.34(s,6H),1.54(d,J=7.2Hz,3H); 13 C NMR (151MHz, CDCl3) δ199.7,139.6,137.4,136.8,134.5,130.0,129.6,128.1,124.7,53.8,21.4,21.2,18.8.

[0122] Example 33: Preparation of Thioesters

[0123]

[0124] Tetraphenylphosphine palladium (11.6 mg) and bis(2-diphenylphosphine) ether (6.5 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), 4-tert-butylstyrene (32.0 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 51.9 mg of a colorless oil, with a yield of 83% (yield calculated based on olefins). NMR characterization data... 1H NMR (600MHz, CDCl3) δ7.35(d,J=7.8Hz,2H),7.27(d,J=7.8Hz,2H),7.22(d,J=7.8Hz,2H),7. 16(d,J=7.8Hz,2H),3.94(q,J=6.6Hz,1H),2.34(s,3H),1.55(d,J=6.6Hz,3H),1.32(s,9H); 13 CNMR (151MHz, CDCl3) δ199.6,150.5,139.5,136.6,134.5,130.0,127.8,125.8,124.7,53.7,34.6,31.5,21.4,18.8.

[0125] Example 34: Preparation of Thioesters

[0126]

[0127] Tetraphenylphosphine palladium (11.6 mg) and bis(2-diphenylphosphine) ether (6.5 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), 4-fluorostyrene (24.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 37.3 mg of a colorless oil, with a yield of 68% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.30-7.32(m,2H),7.17-7.22(m,4H),7.02-7.05(m,2H),3.95(q,J=7.2Hz,1H),2.35(s,3H),1.54(d,J=7.2Hz,3H); 13 C NMR(151MHz,CDCl3)δ199.4,161.6(d,J C-F =246.1Hz),139.7,135.5,134.5,130.1,129.7(d,J C-F =7.6Hz), 124.4, 115.6 (d, J) C-F =21.1Hz), 53.3, 21.4, 18.9; 19 F NMR (376MHz, CDCl3) δ-115.0.

[0128] Example 35: Preparation of Thioesters

[0129]

[0130] Tetraphenylphosphine palladium (11.6 mg) and bis(2-diphenylphosphine) ether (6.5 mg) were added to a 25 mL Young's tube. The reaction tube was transferred three times under nitrogen atmosphere, followed by the sequential addition of dichloromethane (2 mL), 4-bromostyrene (36.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 42.1 mg of a colorless oil, with a yield of 63% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.46(d,J=7.8Hz,2H),7.17-7.24(m,6H),3.93(q,J=6.6Hz,1H),2.35(s,3H),1.53(d,J=7.2Hz,3H); 13 C NMR (151MHz, CDCl3) δ199.0,139.8,138.8,134.5,132.0,130.1,129.8,124.2,121.7,53.5,21.4,18.8.

[0131] Example 36: Preparation of Thioesters

[0132]

[0133] Tris(dibenzylacetone)dipalladium (4.6 mg) and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (7.0 mg) were added to a 25 mL Young's tube. The reaction tube was purged three times under nitrogen, followed by the sequential addition of dichloromethane (2 mL), iodoethane (3 μL), phenylacetylene (20.4 mg), and S-(4-methylphenyl)thiocarbamate (45.6 mg). The reaction flask was sealed and reacted at room temperature for 12 hours under 5 W blue light irradiation. After the reaction, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. Direct column chromatography yielded 44.7 mg of a colorless oil, with a yield of 88% (yield calculated based on olefins). NMR characterization data... 1 H NMR (600MHz, CDCl3) δ7.65 (d, J = 15.6Hz, 1H), 7.54 (m, 2H), 7.39-7.40 (m, 3H), 7. 36(d,J=7.8Hz,2H),7.24(d,J=6.6Hz,2H),6.77(d,J=15.6Hz,1H),2.69(s,3H); 13C NMR (151MHz, CDCl3) δ188.5,141.5,139.8,134.7,134.2,130.8,130.2,129.1,128.6,124.4,124.3,21.5.

[0134] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0135] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0136] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for synthesizing thiocarboxylic acid esters based on unsaturated hydrocarbons, characterized in that, The method includes: mixing unsaturated hydrocarbons, thiocarboxylate (I), metal catalysts, ligands and organic solvents, and reacting them under visible light to synthesize thiocarboxylate (II). Wherein, R is selected from various substituted aryl groups; R 1 R 2 Selected from various substituted aryl or alkyl carbon chains; The R group is an aromatic hydrocarbon substituted with an electron-withdrawing group or an aromatic hydrocarbon substituted with an electron-donating group; the unsaturated hydrocarbon is an olefin or an alkyne. The metal catalyst is selected from one of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium chloride diacetonitrile, tris(dibenzylideneacetone)dipalladium, tetra-triphenylphosphine palladium, palladium chloride dibenzonitrile, and palladium bromide cyclooctadiene. The ligand is selected from 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene and bis(2-diphenylphosphine) ether.

2. The method according to claim 1, characterized in that, R 1 R 2 When substituted for alkyl hydrocarbons, it contains one or more of the following functional groups: halogen, aldehyde, ester, amino, and ketone.

3. The method according to claim 1, characterized in that, The reaction conditions included conducting the synthesis at room temperature.

4. The method according to claim 1, characterized in that, The organic solvent is selected from one of dichloromethane, trichloromethane, toluene, tetrahydrofuran, ethyl acetate, N,N-diethylamide, and anisole; The concentration of the organic solvent is 0.1-1M.

5. The method according to claim 1, characterized in that, The method includes: mixing a metal catalyst and a ligand and converting them under nitrogen, then sequentially adding an organic solvent, an unsaturated hydrocarbon, and a thiocarboxylic acid ester (I); reacting at room temperature under blue light irradiation for 12-24 h; after the reaction is completed, removing the organic solvent by rotary evaporation to obtain the crude product, and then obtaining the thiocarboxylic acid ester (II) by column chromatography.

Images