A new method for preparing thioester compounds using sulfonium salts as raw materials

Abstract

Thioester compounds, as an important generation intermediate, are widely present in bioactive molecules. They are usually used to generate bioactive molecules such as peptides and amino acids. They can also be used in food chemistry and materials science, and play a key role in the regulation and metabolism of cell functions closely related to life. In addition, thioesters can also be used as generation intermediates to generate compounds such as ketones, ethers, alcohols, and amides. Therefore, the generation of thioesters has received widespread attention from chemists. In 2019, we synthesized a new reagent, monothiooxalate, and achieved the thiocarbonylation reaction of halides by palladium catalysis (Org. Lett. 2019, 21, 9521). However, due to the relatively simple structure of halides, the types of thioester compounds synthesized by halides are relatively scarce. In view of this problem, the present invention uses C-H bond functionalization to obtain a wide range of sulfonium salt raw materials, and the sulfonium salt structure type is more novel and diverse. More thioester compounds with different functional groups and more complex structures can be synthesized and prepared, and by this method, the thiocarbonylation reaction of sulfonium salts of different drug molecules can be achieved, and a method is provided for further modification of drug molecules, so the present invention has certain innovation. The present invention provides a new method for preparing thioester compounds by using aryl sulfonium salts as raw materials. Through the reaction characteristics of excited state palladium catalysis, the generation of thioester compounds is carried out under room temperature illumination conditions. The method provided by the present invention can achieve high-efficiency catalytic conversion under room temperature illumination conditions, mild reaction conditions, simple operation, high atomic utilization efficiency, meet the requirements of green environmental friendly chemistry, and the substrate range and functional group compatibility have universality and high chemical selectivity. And the method can be successfully applied to functional group modification of drug molecules to optimize the generation strategy of some drug molecules, improve generation efficiency, reduce reaction costs, and in the form of C-H bond functionalization, the sulfonium salt raw materials obtained are widely available, with good industrial generation value prospects.

Description

Technical Field

[0001] The invention relates to the field of compound generation, and in particular to a new method for preparing a thioester compound by using an aryl sulfonium salt as a raw material under the catalysis of excited state palladium. Background Art

[0002] Thioester compounds are widely present in bioactive molecules as an important intermediate. They are usually used to generate bioactive molecules such as peptides and amino acids. They can also be used in food chemistry and materials science, and play a key role in the regulation of cell functions and metabolism closely related to life. In addition, thioesters can also be used as intermediates to generate compounds such as ketones, ethers, alcohols, and amides. Therefore, the generation of thioesters has received extensive attention from chemists.

[0003] So far, the main method for generating thioester compounds is the thiophenol (alcohol)-carbon monoxide insertion reaction system: under transition metal catalysis, thiophenol (alcohol) is used as a sulfur source, CO is used as a carbonyl source and is combined with hydrocarbon substances to obtain the corresponding thioester. However, due to the participation of toxic CO gas, this method often needs to be carried out under high temperature and high pressure conditions, but in industrial production, the high temperature and high pressure highly toxic production catalytic system is often complicated to operate and highly dangerous. The present invention provides a new method for preparing thioester compounds by using aryl sulfonium salts as raw materials. Through the reaction characteristics of excited state palladium catalysis, thioester compounds are generated under room temperature and light conditions. The method provided by the present invention can achieve high-efficiency catalytic conversion under room temperature and light conditions, and the reaction conditions are milder, the operation is simple, the atomic utilization efficiency is high, and it meets the requirements of green environmentally friendly chemistry. The substrate range and functional group compatibility have universality and high chemical selectivity. This method can be successfully applied to functional group modification of drug molecules to optimize the generation strategy of some drug molecules, improve the generation efficiency, reduce the reaction cost, and the sulfonium salt raw materials obtained by CH bond functionalization are widely available and have good industrial generation value prospects. Summary of the invention

[0004] The problem solved by the present invention is to provide a method for generating a corresponding thioester compound by decarboxylation coupling of an aryl sulfonium salt and oxythioglycolic acid catalyzed by excited state palladium, which only requires the addition of a catalytic amount of a metal reagent, has mild reaction conditions, a wide substrate adaptability range, and good functional group compatibility.

[0005] In order to solve the above technical problems, the technical solution of the present invention is:

[0006] A method for excited state palladium catalyzed decarboxylation coupling of aryl sulfonium salt and oxythioglycolic acid to generate a corresponding thioester compound comprises the following steps:

[0007] At room temperature or under heating conditions, in the presence of a palladium catalyst, a phosphine ligand, an additive and an organic solvent, the corresponding thioester compound is generated by decarboxylation coupling of sulfonium salt and oxythioglycolic acid:

[0008]

[0009] In the general reaction formula shown in the figure above, the catalyst is allylpalladium (II) chloride dimer (Pd Cat) and the phosphine ligand is DPE-Phos.

[0010] Preferably, the molar amount of the catalyst is 5 mol% of the molar amount of Formula 1, Formula 2, and Formula 3.

[0011] Preferably, the molar amount of the phosphine ligand DPE-Phos is 6 mol% of the molar amount of Formula 1, Formula 2, and Formula 3.

[0012] Preferably, the reaction is carried out under illumination at room temperature, in an argon atmosphere, for 12 hours.

[0013] Preferably, the organic solvent is N,N-dimethylacetamide (DMA).

[0014] The method provided by the present invention. In the presence of a palladium catalyst, a phosphine ligand and an organic solvent, an aryl sulfonium salt is coupled with oxythioglycolic acid to generate a corresponding thioester compound, and high-efficiency catalytic conversion can be achieved under room temperature and light conditions, and the reaction conditions are mild, the operation is simple, the atomic utilization efficiency is high, and the requirements of green environmentally friendly chemistry are met. The substrate range and functional group compatibility have universality and high chemical selectivity. Moreover, the method can be successfully applied to functional group modification of drug molecules to optimize the generation strategy of some drug molecules, improve the generation efficiency, reduce the reaction cost, and in the form of CH bond functionalization, the sulfonium salt raw materials obtained have a wide source and have a good industrial generation value prospect. DETAILED DESCRIPTION

[0015] In order to further illustrate the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention. All other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0016] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein can be applied to the methods of the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only.

[0017] In the following examples of the present invention, excited state palladium is used to catalyze the coupling of sulfonium salts with oxythioglycolic acid to generate corresponding thioester compounds. The drugs used are purchased from the following reagent companies:

[0018] N,N-Dimethylacetamide (C4H9NO, 99.5%) was purchased from Adamas Chemicals.

[0019] Bis(2-diphenylphosphinophenyl)ether(C 36 H 28 OP2, 99%) was purchased from Anaiji Chemical Reagent Company.

[0020] Dichloromethane (CH2Cl2, 99%), ethyl acetate (C4H8O2, 99%), petroleum ether, etc. were purchased from Sinopharm Reagent Company.

[0021] The method of generating the corresponding thioester by decarboxylation coupling of sulfonium salt with oxythioglycolic acid by catalyzing excited state palladium in the present invention is carried out in an inert atmosphere such as argon atmosphere. In the process of decarboxylation coupling reaction of excited state palladium sulfonium salt with oxythioglycolic acid, reasonable combination of catalyst and ligand types and selection of solvent are the most important process conditions for the reaction. The inventors have found through a large number of experiments that:

[0022] The molar ratio of the palladium catalyst to the phosphine ligand L1 is 1:1-1:4, more preferably 5:12;

[0023] The reaction time was 12 hours, and the reaction was carried out under light and room temperature in an argon atmosphere.

[0024] The palladium catalyst is preferably allylpalladium chloride (II) dimer, the phosphine ligand is more preferably DPE-Phos, and the organic solvent is more preferably N,N-dimethylacetamide.

[0025] General Procedure A:

[0026] Arylsulfonium salt (1.0 equivalent, 0.2 mmol), oxythioglycolic acid (1.5 equivalent, 0.75 mmol) (if solid), [Pd(allyl)Cl]2 (5 mol%, 1.8 mg) and DPE-Phos (6 mol%, 5.4 mg) were placed in a transparent Schlenk tube (Beijing Xinweier Glass Instrument Co., Ltd., F891410 reaction tube, capacity 10 mL, ground 14 / 20) equipped with a magnetic stirrer. The tube was evacuated and filled with argon (three times). Under argon atmosphere, oxythioglycolic acid (1.5 equivalent, 0.75 mmol) (if liquid) and anhydrous DMA (2.0 mL) were added to these solids through a gastight syringe. The reaction mixture was stirred for 12 hours under light irradiation (450 nm) at room temperature (25°C) (using IKA magnetic stirrer, RCT basic model, stirring speed 600 rpm). The mixture was quenched with saturated NaCl solution and extracted with ethyl acetate (3×20 mL). The organic layers were combined and concentrated in vacuo (Buchhi Rotary Evaporator R-3, Switzerland). The product was purified by silica gel flash column chromatography (Beijing Xinweier Glass Instrument Co., Ltd., C383040C sand plate storage ball chromatography column, 35 / 20, The product was separated by chromatography (petroleum ether / ethyl acetate = 100:1-2:1).

[0027] Example 1. Preparation of S-(p-tolyl) 4-(tert-butyl)phenylthioester

[0028] Reaction:

[0029]

[0030] Using general procedure A, the yield was 92%.

[0031] The S-(p-tolyl)-4-(tert-butyl)phenylthioester obtained in Example 1 was analyzed by nuclear magnetic resonance to obtain the following results:

[0032] 1 H NMR (600MHz, CDCl3) δ7.99–7.94(m,2H),7.49(d,J=8.6Hz,2H),7.39(d,J=8.1Hz,2H),7.25(d,J=7.9Hz,2H),2.39(s,3H),1.34(s,9H).

[0033] 13 C NMR (151MHz, CDCl3) δ190.1,157.5,139.7,135.1,134.1,130.1,127.4,125.7,124.0,35.2,31.1,21.4.

[0034] Example 2: Preparation of S-(p-tolyl)4-(phenyl)phenylthioester

[0035] Reaction:

[0036]

[0037] Using general procedure A, the yield was 95%.

[0038] The S-(p-tolyl)4-(phenyl)phenylthioester obtained in Example 2 was analyzed by nuclear magnetic resonance to obtain the following results:

[0039] 1 H NMR(400MHz, CDCl3)δ8.09(d,J=8.5Hz,2H),7.69(d,J=8.5Hz,2H),7.65–7.58(m,2H) ,7.50–7.43(m,2H),7.39(dd,J=9.6,4.7Hz,3H),7.27(d,J=8.0Hz,2H),2.40(s,3H).

[0040] 13 C NMR (101MHz, CDCl3) δ190.1,146.4,139.9,139.8,135.4,135.1,130.2,129.0,128.4,128.1,127.4,127.3,123.8,21.4.

[0041] Example 3: Preparation of S-(p-tolyl) 4-methyl formate phenylthioester

[0042] Reaction:

[0043]

[0044] Using general procedure A, the yield was 92%.

[0045] The S-(p-tolyl)-4-methyl formate phenylthioester obtained in Example 3 was analyzed by nuclear magnetic resonance to obtain the following results:

[0046] 1 H NMR (600MHz, CDCl3) δ8.14(d,J=8.5Hz,2H),8.07(d,J=8.5Hz,2H),7.39(d,J=8.1Hz,2H),7.28(d,J=7.9Hz,2H),3.96(s,3H),2.41(s,3H).

[0047] 13C NMR (151MHz, CDCl3) δ189.9,151.0,139.7,135.1,134.0,130.1,127.6,125.6,124.1,21.4,15.9,10.5.

[0048] Example 4: Preparation of S-(p-tolyl) 4-phenoxyphenylthioester

[0049] Reaction:

[0050]

[0051] Using general procedure A, the yield was 87%.

[0052] The S-(p-tolyl) 4-phenoxyphenylthioester obtained in Example 4 was analyzed by nuclear magnetic resonance to obtain the following results:

[0053] 1 H NMR (600MHz, CDCl3) δ7.99(d,J=8.8Hz,2H),7.38(t,J=7.9Hz,4H),7.24(d,J=7.9Hz, 2H),7.19(t,J=7.4Hz,1H),7.07(d,J=7.7Hz,2H),7.00(d,J=8.8Hz,2H),2.38(s,3H).

[0054] 13 C NMR (151MHz, CDCl3) δ189.1,162.4,155.4,139.8,135.1,131.2,130.1,130.1,129.7,124.7,123.9,120.3,117.4,21.4.

[0055] Example 5. Preparation of S-(p-tolyl) 2-formylphenyl thioester

[0056] Reaction:

[0057]

[0058] Using general procedure A, the yield was 58%.

[0059] The S-(p-tolyl) 2-formylphenylthioester obtained in Example 5 was analyzed by nuclear magnetic resonance to obtain the following results:

[0060] 1H NMR (600MHz, CDCl3) δ10.37 (s, 1H), 7.84 (dd, J = 7.6, 1.4Hz, 1H), 7.40–7.31 (m, 2 H),7.31–7.24(m,1H),7.21(d,J=7.9Hz,2H),7.02(d,J=8.0Hz,1H),2.38(s,3H).

[0061] 13 C NMR (151MHz, CDCl3) δ191.5,142.8,139.0,134.5,134.0,133.9,133.3,132.2,130.6,130.0,129.4,129.0,125.7,21.3.

[0062] Example 6: Preparation of S-(p-tolyl)4-cyclopropylphenylthioester

[0063] Reaction:

[0064]

[0065] Using general procedure A, the yield was 86%.

[0066] The S-(p-tolyl)4-cyclopropylphenylthioester obtained in Example 6 was analyzed by nuclear magnetic resonance to obtain the following results:

[0067] 1 H NMR (600MHz, CDCl3) δ7.90(d,J=8.3Hz,2H),7.38(d,J=8.0Hz,2H),7.24(d,J=7.9Hz,2H),7 .11(d,J=8.3Hz,2H),2.38(s,3H),2.01–1.86(m,1H),1.09–1.01(m,2H),0.84–0.71(m,2H). 13 C NMR (151MHz, CDCl3) δ189.9,151.0,139.6,135.1,133.9,130.0,127.6,125.6,124.0,21.4,15.8,10.5.

[0068] Example 7: Preparation of S-(p-tolyl) 3-nitrophenyl thioester

[0069] Reaction:

[0070]

[0071] Using general procedure A, the yield was 27%.

[0072] The S-(p-tolyl) 3-nitrobenzene thioester obtained in Example 7 was analyzed by nuclear magnetic resonance to obtain the following results:

[0073] 1 H NMR (400MHz, CDCl3) δ8.42–8.30(m,2H),8.24–8.11(m,2H),7.47–7.37(m,2H),7.30(d,J=7.9Hz,2H),2.43(s,3H).

[0074] 13 C NMR (101MHz, CDCl3) δ189.4,150.6,141.4,140.5,134.9,130.4,128.5,124.0,122.6,21.5.

[0075] Example 8: Preparation of S-(p-tolyl) 2-methoxy-4-acetylphenyl thioester

[0076] Reaction:

[0077]

[0078] Using general procedure A, the yield was 85%.

[0079] The S-(p-tolyl) 2-methoxy-4-acetylphenylthioester obtained in Example 8 was analyzed by nuclear magnetic resonance to obtain the following results:

[0080] 1 H NMR (600MHz, CDCl3) δ8.40 (d, J=2.3Hz, 1H), 8.12 (dd, J=8.8, 2.3Hz, 1H), 7.39 (d, J=8.0Hz ,2H),7.25(d,J=7.8Hz,2H),7.05(d,J=8.8Hz,1H),4.00(s,3H),2.57(s,3H),2.39(s,3H). 13 C NMR (151MHz, CDCl3) δ196.0,189.3,161.5,139.8,134.8,133.9,130.8,130.1,129.9,126.3,124.7,111.9,56.2,26.4,21.4.

[0081] Example 9: Preparation of S-(p-toluene)benzo[d][1,3]dioxolane-5-carbothioate

[0082] Reaction:

[0083]

[0084] Using general procedure A, the yield was 95%.

[0085] The S-(p-toluene)benzo[d][1,3]dioxolane-5-thiocarboxylate obtained in Example 9 was analyzed by nuclear magnetic resonance to obtain the following results: 1 H NMR (400MHz, CDCl3) δ7.83(dd,J=7.8,1.6Hz,1H),7.47(ddd,J=10.5,6.1,1.5Hz,2H),7.37(d,J=8.0Hz,2H),7.23(d,J=8.1Hz ,2H),7.13(d,J=8.3Hz,1H),7.08–7.01(m,1H),6.50(d,J=3.2Hz,1H),6.37(dd,J=3.2,1.9Hz,1H),5.17(s,2H),2.38(s,3H).

[0086] 13 C NMR (101MHz, CDCl3) δ189.7,157.0,149.7,143.1,139.5,134.9,133.7,130.0,129.9,127.4,125.3,121.4,114.4,110.6,110.5,63.8,21.4.

[0087] Example 10: Preparation of S-(p-toluene) 3-bromo-4-trifluoromethylphenylthioester

[0088] Reaction:

[0089]

[0090] Using general procedure A, the yield was 68%.

[0091] The S-(p-toluene) 3-bromo-4-trifluoromethylphenylthioester obtained in Example 10 was analyzed by nuclear magnetic resonance to obtain the following results:

[0092] 1 H NMR (600MHz, CDCl3) δ7.77(m,J=18.3,7.4Hz,2H),7.65–7.59(m,2H),7.40(d,J=7.9Hz,2H),7.27(d,J=8.0Hz,2H),2.39(s,3H).

[0093] 13C NMR(151MHz,Chloroform-d)δ191.7,140.2,137.6,134.6,131.8,131.1,130.3,128.4 ,127.4(dd,J=65.7,33.1Hz),127.0(q,J=5.1Hz),123.7,123.3(q,J=274.1Hz),21.4.

[0094] Example 11: Preparation of S-(p-toluene)quinoline-7-phenylthioester

[0095] Reaction:

[0096]

[0097] Using general procedure A, the yield was 52%.

[0098] The S-(p-toluene)quinoline-7-phenylthioester obtained in Example 11 was analyzed by nuclear magnetic resonance to obtain the following results:

[0099] 1 H NMR (400MHz, CDCl3) δ9.03 (d, J = 2.8Hz, 1H), 8.57 (s, 1H), 8.39–8.10 (m, 3H), 7.57–7.37 (m, 3H), 7.34–7.16 (m, 2H), 2.41 (s, 3H).

[0100] 13 C NMR (101MHz, CDCl3) δ190.1,152.6,150.1,140.1,137.8,135.0,134.6,130.3,130.1,128.7,127.5,127.2,123.4,122.2,21.4.

[0101] Example 12: Preparation of S-(p-toluene)thiophene-2-carbothioate

[0102] Reaction:

[0103]

[0104] Using general procedure A, the yield was 61%.

[0105] The S-(p-toluene)thiophene-2-carbothioate obtained in Example 12 was analyzed by nuclear magnetic resonance to obtain the following results:

[0106] 1H NMR (600MHz, CDCl3) δ7.89 (m, J=3.8, 0.9Hz, 1H), 7.65 (m, J=5.0, 0.9Hz, 1H), 7.4 0(d,J=8.1Hz,2H),7.28–7.22(m,2H),7.15(dd,J=4.8,4.0Hz,1H),2.39(s,3H).

[0107] 13 C NMR (151MHz, CDCl3) δ182.5,141.5,134.0,135.0,133.1,131.5,130.1,128.0,123.4,21.4.

[0108] Example 13: Preparation of S-(p-chlorophenyl) 4-tert-butylphenyl thioester

[0109] Reaction:

[0110]

[0111] Using general procedure A, the yield was 67%.

[0112] The S-(p-chlorophenyl) 4-tert-butylphenylthioester obtained in Example 13 was analyzed by nuclear magnetic resonance to obtain the following results:

[0113] 1 H NMR (600MHz, CDCl3) δ7.95 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 3.7 Hz, 4H), 1.35 (s, 9H).

[0114] 13 C NMR (151MHz, CDCl3) δ189.1,157.8,136.3,135.9,133.8,129.5,127.5,126.1,125.8,35.3,31.0.

[0115] Example 14: Preparation of S-(p-fluorophenyl) 4-tert-butylphenyl thioester

[0116] Reaction:

[0117]

[0118] Using general procedure A, the yield was 75%.

[0119] The S-(p-fluorophenyl) 4-tert-butylphenylthioester obtained in Example 14 was analyzed by nuclear magnetic resonance to obtain the following results:

[0120] 1H NMR (600MHz, CDCl3) δ7.95 (d, J=8.5Hz, 2H), 7.61–7.37 (m, 4H), 7.21–

[0121] 6.97(m,2H),1.35(s,9H).

[0122] 13 C NMR (151 MHz, CDCl3) δ 189.6, 163.6 (d, J = 250.0 Hz), 157.7, 137.2 (d, J = 8.6 Hz), 133.8, 127.5, 125.8, 122.9 (d, J = 3.4 Hz), 116.5 (d, J = 22.1 Hz), 35.3, 31.1. Example 15. Preparation of S-(p-bromophenyl) 4-tert-butylphenyl thioester

[0123] Reaction:

[0124]

[0125] Using general procedure A, the yield was 54%.

[0126] The S-(p-bromophenyl) 4-tert-butylphenylthioester obtained in Example 15 was analyzed by nuclear magnetic resonance to obtain the following results:

[0127] 1 H NMR (600MHz, CDCl3) δ7.87(d,J=8.5Hz,2H),7.51–7.47(m,2H),7.42(d,J=8.5Hz,2H),7.29(d,J=8.4Hz,2H),1.27(s,9H).

[0128] 13 C NMR (151MHz, CDCl3) δ187.9,156.8,135.5,132.7,131.4,126.4,125.8,124.8,123.1,34.2,30.1.

[0129] Example 16: Preparation of S-(p-trifluoromethylphenyl)4-tert-butylphenylthioester

[0130] Reaction:

[0131]

[0132] Using general procedure A, the yield was 74%.

[0133] The S-(p-trifluoromethylphenyl)4-tert-butylphenylthioester obtained in Example 16 was analyzed by nuclear magnetic resonance to obtain the following results:

[0134] 1 H NMR (600MHz, CDCl3) δ7.96(d,J=8.4Hz,2H),7.70(d,J=8.2Hz,2H),7.64(d,J=8.2Hz,2H),7.52(d,J=8.4Hz,2H),1.36(s,9H).

[0135] 13 C NMR (151MHz, CDCl3) δ188.4, 158.1, 135.2, 133.6, 132.5, 131.4 (q, J = 32.7Hz), 127.5, 125.9 (q, J = 3.7Hz), 125.9, 123.9 (d, J = 272.4Hz), 35.3, 31.1.

[0136] Example 17: Preparation of S-(p-methoxyphenyl) 4-tert-butylphenyl thioester

[0137] Reaction:

[0138]

[0139] Using general procedure A, the yield was 97%.

[0140] The S-(p-methoxyphenyl) 4-tert-butylphenylthioester obtained in Example 17 was analyzed by nuclear magnetic resonance to obtain the following results:

[0141] 1 H NMR (600MHz, CDCl3) δ7.96 (d, J = 8.5 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.8 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H), 1.34 (s, 9H).

[0142] 13 C NMR (151MHz, CDCl3) δ190.6,160.8,157.4,136.7,134.1,127.4,125.7,118.2,115.0,55.4,35.2,31.1.

[0143] Example 18: Preparation of S-(2-methylbenzoate)-4-tert-butylphenylthioester

[0144] Reaction:

[0145]

[0146] Using general procedure A, the yield was 73%.

[0147] The S-(2-methylbenzoate)-4-tert-butylphenylthioester obtained in Example 18 was analyzed by nuclear magnetic resonance to obtain the following results:

[0148] 1 H NMR (600MHz, CDCl3) δ7.97 (m J=7.8,1.2Hz,1H),7.49(d,J=8.3Hz,2H),7.45(d,J=8.4Hz,2H),7.25(m,J=6.2,4 .9Hz,1H),7.10(t,J=7.3Hz,1H),6.82(d,J=8.1Hz,1H),3.95(s,3H),1.36(s,9H).

[0149] 13 C NMR (151MHz, CDCl3) δ166.9,152.5,143.9,135.5,132.3,131.0,128.7,127.2,126.8,126.5,124.0,52.2,34.8,31.3.

[0150] Example 19: Preparation of S-(2-naphthyl)4-tert-butylphenylthioester

[0151] Reaction:

[0152]

[0153] Using general procedure A, the yield was 82%.

[0154] The S-(2-naphthyl)4-tert-butylphenylthioester obtained in Example 19 was analyzed by nuclear magnetic resonance to obtain the following results:

[0155] 1 H NMR (600MHz, CDCl3) δ8.16 (s, 1H), 8.11 (d, J = 8.4Hz, 2H), 8.04–7.94 (m, 3H), 7.68–7.59 (m, 5H), 1.47 (s, 9H).

[0156] 13 C NMR (151MHz, CDCl3) δ189.9,157.6,135.0,134.1,133.7,133.4,131.5,128.8,128.0,127.8,127.5,127.1,126.5,125.8,125.0,35.3,31.1.

[0157] Example 20: Preparation of S-(2,4-dimethylphenyl)4-(tert-butyl)phenylthioester

[0158] Reaction:

[0159]

[0160] Using general procedure A, the yield was 85%.

[0161] The S-(2,4-dimethylphenyl)4-(tert-butyl)phenylthioester obtained in Example 20 was analyzed by nuclear magnetic resonance to obtain the following results:

[0162] 1 H NMR (600MHz, CDCl3) δ7.99(d,J=8.5Hz,2H),7.49(d,J=8.5Hz,2H),7.35(d,J=7.8Hz, 1H),7.17(s,1H),7.07(d,J=7.7Hz,1H),2.35(d,J=9.4Hz,6H),1.36(d,J=7.1Hz,9H).

[0163] 13 C NMR (151MHz, CDCl3) δ189.6,157.3,142.4,140.3,136.3,134.3,131.7,127.5,127.5,125.7,123.5,35.2,31.1,21.3,20.7.

[0164] Example 21. Preparation of S-phenylethyl ester of 4-(tert-butyl)phenylene sulfide

[0165] Reaction:

[0166]

[0167] Using general procedure A, the yield was 85%.

[0168] The S-phenethyl ester of 4-(tert-butyl)phenylene sulfide obtained in Example 21 was analyzed by nuclear magnetic resonance to obtain the following results:

[0169] 1 H NMR (600MHz, CDCl3) δ7.82 (dd, J=8.5, 2.1Hz, 1H), 7.39–7.34 (m, 1H), 7.23 (t, J=7.4Hz, 1H), 7. 19(d,J=7.4Hz,1H),7.17–7.14(m,1H),3.26–3.19(m,1H),2.88(t,J=7.7Hz,1H),1.25(s,6H).

[0170] 13C NMR (151MHz, CDCl3) δ191.4,157.1,140.2,134.5,128.7,128.5,127.1,126.5,125.5,36.0,35.2,31.1,30.3.

[0171] Example 22: Preparation of 4-(tert-butyl)benzyl thiocarboxylate

[0172] Reaction:

[0173]

[0174] Using general procedure A, the yield was 65%.

[0175] The 4-(tert-butyl)benzyl thiocarboxylate obtained in Example 22 was analyzed by nuclear magnetic resonance to obtain the following results:

[0176] 1 H NMR (600MHz, CDCl3) δ7.83(d,J=8.1Hz,2H),7.37(d,J=8.4Hz,2H),7.29(d,J=7.6H z,2H),7.22(t,J=7.6Hz,2H),7.16(m,J=8.5,6.1Hz,1H),4.23(s,2H),1.24(s,9H).

[0177] 13 C NMR (151MHz, CDCl3) δ189.8,156.3,136.6,128.0,127.6,126.2,126.2,124.6,76.2,76.0,75.8,34.1,32.2,30.1.

[0178] Example 23: Preparation of 4-(tert-butyl)phenylene sulfide-S-cyclohexane

[0179] Reaction:

[0180]

[0181] Using general procedure A, the yield was 72%.

[0182] The 4-(tert-butyl)phenylene sulfide-S-cyclohexane obtained in Example 23 was analyzed by nuclear magnetic resonance to obtain the following results:

[0183] 1H NMR (600MHz, CDCl3) δ7.81(d,J=8.5Hz,2H),7.37(d,J=8.5Hz,2H),3.65(dd,J=8.5,4.5Hz,1H),2. 04–1.88(m,2H),1.68(dd,J=9.4,4.1Hz,2H),1.61–1.51(m,1H),1.50–1.35(m,4H),1.26(s,10H).

[0184] 13 C NMR (151MHz, CDCl3) δ191.5,156.9,134.9,127.1,125.5,42.4,35.1,33.3,31.1,26.1,25.7.

[0185] Example 24: Preparation of 4-(tert-butyl)phenylene sulfide-S-tert-butane

[0186] Reaction:

[0187]

[0188] Using general procedure A, the yield was 58%.

[0189] The 4-(tert-butyl)phenylene sulfide-S-tert-butane obtained in Example 24 was analyzed by nuclear magnetic resonance to obtain the following results:

[0190] 1 H NMR (600MHz, CDCl3) δ7.85 (d, J = 8.5 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H), 1.57 (s, 9H), 1.33 (s, 9H).

[0191] 13 C NMR (151MHz, CDCl3) δ192.5,156.6,135.7,126.9,125.4,48.0,35.1,31.1,30.1.

[0192] The above is a detailed introduction to the method provided by the present invention for the decarboxylation coupling of an arylsulfonium salt with oxythioacetic acid to generate a corresponding thioester by catalyzing an excited state palladium. Specific examples are used herein to illustrate the principle and implementation of the invention, and the description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, the present invention can also be improved and modified in a number of ways without departing from the principle of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a thioester compound by using an arylsulfonium salt as a raw material, characterized in that: Under light irradiation and room temperature, in the presence of a palladium catalyst, a phosphine ligand and an organic solvent, the corresponding thioester compound is prepared by decarboxylation cross-coupling of a sulfonium salt and oxythioglycolic acid, and the reaction formula is as follows: The catalyst is allylpalladium chloride (II) dimer, and the phosphine ligand is DPE-Phos; the molar amount of the palladium catalyst allylpalladium chloride (II) dimer is 5 mol% of the molar amount of the S-1, S-2, and S-3; the molar amount of the phosphine ligand DPE-Phos is 6 mol% of the molar amount of the S-1, S-2, and S-3; the reaction is carried out under 450nm blue LEDs illumination and room temperature, the reaction atmosphere is under argon protection, and the reaction time is 12 hours; the organic solvent is N,N-dimethylacetamide, and the amount is 2.0 mL.

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