Synthetic method and application for constructing new C-C bonds by copper-catalyzed cross-coupling reaction of aryl sulfonium salts and arylsilanes

Abstract

The present invention discloses a synthetic method for constructing a new C-C bond by the copper-catalyzed cross-coupling reaction of arylsulfonium salts with arylsilanes. The method uses arylsulfonium salts and arylsilanes as reaction raw materials, arylsulfonium salts as electrophilic reagents, and arylsilanes as nucleophilic reagents to synthesize biaryl compounds under the conditions of a catalyst / ligand / base / solvent. Among them, the catalyst is cuprous iodide, and 1,10-Phen and cesium fluoride are used as additives to achieve the synthesis of biaryl compounds at 70 °C. The reaction of the method of the present invention avoids the use of aryl halides and reduces environmental pollution. In addition, the reaction uses arylsulfonium salts as electrophilic reagents, improving the site selectivity of the reaction. The reaction avoids the use of organometallic reagents, avoiding the toxicity and instability of organometallic reagents. The reaction avoids the use of precious metal catalysts and uses inexpensive cuprous iodide as a metal catalyst, reducing the cost of synthesizing biaryl compounds.

Description

Technical Field

[0001] The present invention belongs to the technical field of constructing new C-C bonds, and in particular to a synthetic method and application for constructing new C-C bonds by copper-catalyzed cross-coupling reaction of aryl sulfonium salts and arylsilanes. Background Art

[0002] Biaryl fragments (Ar1-Ar2) are one of the most important functional groups in pharmaceuticals, pesticides, and organic functional materials. Therefore, the synthetic method of catalytic cross-coupling reaction to construct new C-C bonds has always been a research hotspot.

[0003] Biaryl fragments are generally synthesized by cross-coupling reactions of organohalides catalyzed by noble metals with organometallic reagents. However, organometallic reagents have the disadvantages of high toxicity and instability, noble metal catalysts are expensive, and organohalides are toxic. Therefore, developing a method for synthesizing biaryl fragments that is non-toxic, environmentally friendly, highly selective, and inexpensive has always been a research hotspot for scientists. Recently, some scientists have used highly regioselective organosulfonium salts instead of organohalides as electrophiles to achieve the construction of biaryl fragments, but scientists still use noble metals as catalysts. Organosilanes have the characteristics of low toxicity, stability, and excellent solubility, and their cross-coupling reactions as nucleophiles have also received extensive attention in recent years.

[0004] Through retrieval, no patent publication documents related to the present invention patent application have been found. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a synthetic method and application for constructing new C-C bonds by copper-catalyzed cross-coupling reaction of aryl sulfonium salts and arylsilanes.

[0006] The technical solution adopted by the present invention to solve its technical problems is as follows:

[0007] A synthetic method for constructing new C-C bonds by copper-catalyzed cross-coupling reaction of aryl sulfonium salts and arylsilanes. The method uses aryl sulfonium salts and arylsilanes as reaction raw materials, aryl sulfonium salts as electrophiles, and arylsilanes as nucleophiles to synthesize biaromatic compounds under the conditions of catalyst / ligand / base / solvent; wherein, the catalyst is cuprous iodide, and 1,10-phenanthroline (i.e., 1,10-Phen) and cesium fluoride are used as additives to achieve the synthesis of biaromatic compounds at 70 °C.

[0008] Furthermore, the reaction general formula of the method is as follows:

[0009]

[0010] Wherein, Ar1 and Ar2 represent the same or different aryl systems.

[0011] Further, the aryl sulfonium salt is any one of the following compounds:

[0012]

[0013]

[0014] wherein R, R1, and R2 are independent C1-C 15 alkyl chains, and the C1-C 15 alkyl chain includes a straight-chain alkyl group with 1 to 15 carbon atoms, a branched-chain alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 8 carbon atoms.

[0015] Further, the straight-chain alkyl group with 1 to 15 carbon atoms includes: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; the branched-chain alkyl group with 3 to 15 carbon atoms includes: isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl; the cycloalkyl group with 3 to 8 carbon atoms includes: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

[0016] Further, the arylsilane is any one of the following compounds:

[0017]

[0018] wherein R is an independent C1-C 15 alkyl chain, and the C1-C 15 alkyl chain includes a straight-chain alkyl group with 1 to 15 carbon atoms, a branched-chain alkyl group with 3 to 15 carbon atoms, and a cycloalkyl group with 3 to 8 carbon atoms.

[0019] Further, the straight-chain alkyl groups with 1-15 carbon atoms include: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; the branched-chain alkyl groups with 3-15 carbon atoms include: isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl; the cycloalkyl groups with 3-8 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

[0020] Further, the method includes the following steps:

[0021] (1) Under the protection of an inert gas, in the catalytic action of CuI, 1,10-Phen and cesium fluoride are added as additives, and the aryl sulfonium salt and arylsilane are placed in N,N-dimethylformamide for reaction to obtain a mixture;

[0022] (2) Dichloromethane and silica gel powder are added to the reaction system, then the organic solvent is removed under reduced pressure, and finally a pure product is obtained through a flash column chromatography machine.

[0023] Further, the method includes the following steps:

[0024] 1.0 equivalent of aryl sulfonium salt, 1.5 equivalents of arylsilane, CuI, 1,10-Phen, and 1.5 equivalents of cesium fluoride are placed in a reaction flask. The addition amount of CuI is 80.0 mol% of the total molar amount of the aryl sulfonium salt, and the addition amount of 1,10-Phen is 10.0 mol% of the total molar amount of the aryl sulfonium salt; after displacing nitrogen three times, dry N,N-dimethylformamide is added to keep the concentration of the solution, that is, the concentration of the aryl sulfonium salt in N,N-dimethylformamide, at 0.5 M; after stirring at 70 °C for 14 hours, dichloromethane and silica gel powder are added to the reaction system, then the organic solvent is removed under reduced pressure, and finally a pure product is obtained through a flash column chromatography machine.

[0025] Use of the synthesis method as described above in the post-modification of drugs and / or asymmetric cross-coupling reactions.

[0026] The advantages and positive effects obtained by the present invention are:

[0027] 1. The reaction of the method of the present invention avoids the use of aryl halides, reducing environmental pollution. Additionally, the reaction uses aryl sulfonium salts as electrophilic reagents, which have high site selectivity, thus improving the site selectivity of the reaction. The reaction avoids the use of organometallic reagents, avoiding the toxicity and instability of organometallic reagents. The reaction also avoids the use of noble metal catalysts and uses inexpensive copper iodide as the metal catalyst, reducing the cost of synthesizing biaryl compounds.

[0028] The relevant advantages of the method of the present invention can be directly seen from the following reaction formula.

[0029]

[0030] 2. The method of the present invention can be applied to the post-modification of drugs. It can be directly seen from the following reaction formula:

[0031]

[0032] 3. The reaction of the method of the present invention can be applied to a reaction system of more than one gram, obtaining a yield equivalent to that of a microscale reaction. As Figure 1 shown. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a proof diagram that the reaction of the method of the present invention can be applied to a reaction system of more than one gram and can obtain a yield equivalent to that of a microscale reaction. DETAILED DESCRIPTION OF THE INVENTION

[0034] The following further illustrates the present invention in conjunction with embodiments. The following embodiments are narrative and not restrictive, and the protection scope of the present invention cannot be limited by the following embodiments.

[0035] All kinds of experimental operations involved in the specific embodiments are conventional techniques in the art. For the parts not specifically noted herein, those of ordinary skill in the art can refer to various commonly used reference books, scientific and technological literatures, or relevant specifications, manuals, etc. before the filing date of the present invention application for implementation.

[0036] A synthetic method for constructing a new C-C bond by copper-catalyzed cross-coupling reaction of aryl sulfonium salts and arylsilanes. The method uses aryl sulfonium salts and arylsilanes as reaction raw materials, aryl sulfonium salts as electrophilic reagents, and arylsilanes as nucleophilic reagents to synthesize biaryl compounds under the conditions of catalyst / ligand / base / solvent. Among them, the catalyst is copper iodide, and 1,10-phenanthroline (i.e., 1,10-Phen) and cesium fluoride are used as additives to achieve the synthesis of biaryl compounds at 70 °C.

[0037] Preferably, the reaction general formula of the method is as follows:

[0038]

[0039] Among them, Ar1 and Ar2 represent the same or different aryl systems. Preferably, the aryl sulfonium salt is any one of the following compounds:

[0040]

[0041]

[0042] Among them, R, R1, and R2 are independent C1-C 15 alkyl chains, and the C1-C 15 alkyl chain includes a straight-chain alkyl group with a total number of carbon atoms of 1-15, a branched-chain alkyl group with a total number of carbon atoms of 3-15, or a cycloalkyl group with a total number of carbon atoms of 3-8.

[0043] Preferably, the straight-chain alkyl group with a total number of carbon atoms of 1-15 includes: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; the branched-chain alkyl group with a total number of carbon atoms of 3-15 includes: isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl; the cycloalkyl group with a total number of carbon atoms of 3-8 includes: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

[0044] Preferably, the arylsilane is any one of the following compounds:

[0045]

[0046] Among them, R is an independent C1-C 15 alkyl chain, and the C1-C 15 alkyl chain includes a straight-chain alkyl group with a total number of carbon atoms of 1-15, a branched-chain alkyl group with a total number of carbon atoms of 3-15, and a cycloalkyl group with a total number of carbon atoms of 3-8.

[0047] Preferably, the straight-chain alkyl groups with 1-15 carbon atoms include: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; the branched-chain alkyl groups with 3-15 carbon atoms include: isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl; the cycloalkyl groups with 3-8 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

[0048] Preferably, the method comprises the following steps:

[0049] (1) Under the protection of an inert gas, in the presence of CuI as a catalyst, 1,10-Phen and cesium fluoride are added as additives, and the aryl sulfonium salt and arylsilane are placed in N,N-dimethylformamide for reaction to obtain a mixture;

[0050] (2) Dichloromethane and silica gel powder are added to the reaction system, then the organic solvent is removed under reduced pressure, and finally a pure product is obtained by a flash column chromatography machine.

[0051] Preferably, the method comprises the following steps:

[0052] 1.0 equivalent of aryl sulfonium salt, 1.5 equivalents of arylsilane, CuI, 1,10-Phen, and 1.5 equivalents of cesium fluoride are placed in a reaction flask. The addition amount of CuI is 80.0 mol% of the total molar amount of the aryl sulfonium salt, and the addition amount of 1,10-Phen is 10.0 mol% of the total molar amount of the aryl sulfonium salt; after displacing nitrogen three times, dry N,N-dimethylformamide is added to keep the concentration of the solution, that is, the concentration of the aryl sulfonium salt in N,N-dimethylformamide, at 0.5 M; after stirring at 70 °C for 14 hours, dichloromethane and silica gel powder are added to the reaction system, then the organic solvent is removed under reduced pressure, and finally a pure product is obtained by a flash column chromatography machine. Application of the synthesis method as described above in the post-modification of drugs and / or asymmetric cross-coupling reactions.

[0053] Specifically, the related preparation and detection are as follows:

[0054] Example 1

[0055]

[0056] 1.0 equivalent of benzene-derived dibenzothiophenium salt (0.2 mmol, 82.3 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (37.8 mg, 90%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.84 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 7.4 Hz, 1H), 7.76–7.68 (m, 2H), 7.56 (s, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.39–7.28 (m, 3H). 13 C NMR (126 MHz, CDCl3): δ 144.23, 140.68, 139.49, 134.29, 128.93, 128.24, 126.48, 124.49, 124.29, 123.55, 122.25, 119.44.

[0057] Example 2

[0058]

[0059] 1.0 equivalent of isopropylbenzene-derived dibenzothiophenium salt (0.2 mmol, 90.7 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (40.4 mg, 80%) was obtained by flash column chromatography. 11H NMR (500 MHz, CDCl3): δ 7.81 (d, J = 7.9 Hz, 1H), 7.75 (d, J = 7.7 Hz, 1H), 7.64 (d, J = 8.1 Hz, 2H), 7.50 (s, 1H), 7.31 (dt, J = 22.4, 7.5 Hz, 4H), 2.94 (hept, J = 6.9 Hz, 1H), 1.28 (d, J = 6.9 Hz, 6H). 13 13C NMR (126 MHz, CDCl3): δ 149.24, 144.38, 140.75, 139.33, 131.85, 127.01, 126.47, 124.41, 124.08, 123.39, 122.22, 118.85, 33.90, 23.89. HRMS (EI) m / z calcd for C 17 H 16 S [M] + : 252.0973, found 252.0967.

[0060] Example 3

[0061]

[0062] 1.0 equivalent of tert-butylbenzene-derived dibenzothiophenium salt (0.5 mmol, 350.2 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.75 mmol, 186.3 mg), CuI (0.4 mmol, 76.7 mg), 1,10-phenanthroline (0.05 mmol, 9.6 mg), and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.3 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 h, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (113.5 mg, 86%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.82 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 7.7 Hz, 1H), 7.66 (d, J = 8.4 Hz, 2H), 7.52 (s, 1H), 7.46 (d, J = 8.4 Hz, 2H), 7.37–7.32 (m, 1H), 7.32–7.28 (m, 1H), 1.36 (s, 9H). 1313C NMR (126 MHz, CDCl3): δ 151.47, 144.30, 140.77, 139.38, 131.48, 126.20, 125.87, 124.41, 124.09, 123.41, 122.22, 118.89, 34.67, 31.24.

[0063] Example 4

[0064]

[0065] 1.0 equivalent of cyclohexylbenzene-derived dibenzothiophenium salt (0.2 mmol, 98.8 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.9 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (40.9 mg, 70%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.82 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 7.7 Hz, 1H), 7.64 (d, J = 8.2 Hz, 2H), 7.51 (s, 1H), 7.36–7.32 (m, 1H), 7.32–7.26 (m, 3H), 2.57–2.51 (m, 1H), 2.00–1.70 (m, 5H), 1.52–1.19 (m, 5H). 13 13C NMR (126 MHz, CDCl3): δ 148.46, 144.42, 140.76, 139.33, 131.84, 127.39, 126.43, 124.40, 124.06, 123.38, 122.21, 118.81, 44.32, 34.33, 26.83, 26.10. HRMS (EI) m / z calcd for C 20 H 20 S [M] + : 292.1286, found 292.1281.

[0066] Example 5

[0067]

[0068] 1.0 equivalent of fluorobenzene-derived dibenzothiophenium salt (0.5 mmol, 214.5 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.75 mmol, 186.2 mg), CuI (0.4 mmol, 76.7 mg), 1,10-phenanthroline (0.05 mmol, 9.4 mg), and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.3 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (99.2 mg, 87%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.83 (d, J = 7.9 Hz, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.72–7.63 (m, 2H), 7.47 (s, 1H), 7.41–7.29 (m, 2H), 7.16–7.08 (m, 2H). 13 C NMR (126 MHz, CDCl3): δ 163.73, 161.76, 143.03, 140.64, 139.42, 130.56, 128.15 (d, J = 8.2 Hz), 124.47 (d, J = 28.9 Hz), 123.52, 122.22, 119.42, 115.92 (d, J = 21.9 Hz). 19 F NMR (471 MHz, CDCl3): δ -113.22.

[0069] Example 6

[0070]

[0071] 1.0 equivalent of chlorobenzene-derived dibenzothiophenium salt (0.2 mmol, 89.2 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (33.3 mg, 68%) was obtained by flash column chromatography. 11H NMR (500 MHz, CDCl3): δ 7.83 (d, J = 7.9 Hz, 1H), 7.78 (d, J = 7.7 Hz, 1H), 7.64 (d, J = 8.4 Hz, 2H), 7.53 (s, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.35 (dt, J = 18.4, 7.3 Hz, 2H). 13 13C NMR (126 MHz, CDCl3): δ 142.82, 140.57, 139.49, 134.08, 132.83, 129.11, 127.63, 124.65, 124.57, 123.65, 122.27, 119.87.

[0072] Example 7

[0073]

[0074] 1.0 equivalent of benzoate-derived dibenzothiophenium salt (0.5 mmol, 241.8 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.75 mmol, 186.3 mg), CuI (0.4 mmol, 76.9 mg), 1,10-phenanthroline (0.05 mmol, 9.5 mg) and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.2 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (114.2 mg, 81%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 8.39 (s, 1H), 8.02 (d, J = 7.7 Hz, 1H), 7.89 (d, J = 7.9 Hz, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.80 (d, J = 7.4 Hz, 1H), 7.64 (s, 1H), 7.51 (t, J = 7.7 Hz, 1H), 7.41–7.30 (m, 2H), 4.43 (q, J = 7.1 Hz, 2H), 1.44 (t, J = 7.1 Hz, 3H). 13 13C NMR (126 MHz, CDCl3): δ 166.21, 142.99, 140.54, 139.57, 134.58, 131.25, 130.57, 129.11, 128.99, 127.36, 124.63, 124.61, 123.74, 122.29, 120.22, 61.23, 14.35. HRMS (EI) m / z calcd for C 17 H14 O2S[M] + : 282.0715, found 282.0711。

[0075] Example 8

[0076]

[0077] 1.0 equivalent of 4 - methoxybenzonitrile - derived dibenzothiophene sulfonium salt (0.2 mmol, 93.4 mg), 1.5 equivalents of 2 - triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.7 mg), 1,10 - phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N - dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (33.4 mg, 63%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.98 (s, 1H), 7.85 (d, J = 7.3 Hz, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.77 (s, 1H), 7.62 (d, J = 8.5 Hz, 1H), 7.36 (p, J = 6.9 Hz, 2H), 7.07 (d, J = 8.6 Hz, 1H), 4.04 (s, 3H). 13 CNMR (126 MHz, CDCl3): δ 159.23, 139.85, 139.67, 137.18, 133.07, 133.02, 124.74, 124.54, 124.43, 123.82, 123.79, 121.86, 118.78, 111.99, 104.49, 55.94. HRMS (EI) m / z calcd for C 16 H 11 NOS[M] + : 265.0561, found 265.0557。

[0078] Example 9

[0079]

[0080] 1.0 equivalent of 1,2-dimethoxybenzene-derived dibenzothiophenium salt (0.5 mmol, 235.4 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.75 mmol, 186.3 mg), CuI (0.4 mmol, 76.7 mg), 1,10-phenanthroline (0.05 mmol, 9.4 mg), and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.3 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (115.9 mg, 86%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.81 (d, J = 7.9 Hz, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.44 (s, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.32–7.27 (m, 2H), 7.22 (d, J = 1.8 Hz, 1H), 6.92 (d, J = 8.3 Hz, 1H), 3.98 (s, 1H), 3.93 (s, 1H). 13 C NMR (126 MHz, CDCl3): δ 149.40, 149.20, 144.24, 140.79, 139.18, 127.34, 124.47, 124.02, 123.26, 122.15, 119.29, 118.45, 111.45, 109.69, 55.99.

[0081] Example 10

[0082]

[0083] 1.0 equivalent of methyl 2-methoxybenzoate-derived dibenzothiophenium salt (0.2 mmol, 99.9 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.7 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (47.7 mg, 80%) was obtained by flash column chromatography. 11H NMR (500 MHz, CDCl3): δ 8.15 (d, J = 2.4 Hz, 1H), 7.84–7.78 (m, 2H), 7.76 (d, J = 7.7 Hz, 1H), 7.48 (s, 1H), 7.35 (t, J = 7.4 Hz, 1H), 7.30 (t, J = 7.4 Hz, 1H), 7.04 (d, J = 8.7 Hz, 1H), 3.96 (s, 1H), 3.94 (s, 1H). 13 13C NMR (126 MHz, CDCl3): δ 166.24, 159.07, 142.83, 140.73, 139.28, 131.32, 129.68, 126.72, 124.58, 124.25, 123.44, 122.22, 120.49, 118.99, 112.55, 56.24, 52.22. HRMS (EI) m / z calcd for C 17 H 14 O3S [M] + : 298.0664, found 298.0657.

[0084] Example 11

[0085]

[0086] 1.0 equivalent of 4-phenylbutyrate-derived dibenzothiophenium salt (0.2 mmol, 102.3 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After purging with nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 h, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvents were removed under reduced pressure. A white solid (42.5 mg, 69%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.82 (d, J = 7.8 Hz, 1H), 7.77 (d, J = 7.7 Hz, 1H), 7.64 (d, J = 8.1 Hz, 2H), 7.51 (s, 1H), 7.35 (t, J = 7.1 Hz, 1H), 7.30 (t, J = 7.1 Hz, 1H), 7.24 (d, J = 8.1 Hz, 2H), 3.68 (s, 3H), 2.70 (t, J = 7.6 Hz, 2H), 2.37 (t, J = 7.4 Hz, 2H), 2.00 (p, J = 7.4 Hz, 2H). 1313C NMR (126 MHz, CDCl3): δ 173.82, 144.18, 141.68, 140.71, 139.33, 132.09, 129.04, 126.48, 124.43, 124.14, 123.41, 122.20, 118.98, 51.52, 34.78, 33.29, 26.30. HRMS (EI) m / z calcd for C 19 H 18 O2S [M] + : 310.1028, found 310.1023.

[0087] Example 12

[0088]

[0089] 1.0 equivalent of 1,3,5-trimethylbenzene-derived dibenzothiophenium salt (0.5 mmol, 226.5 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.75 mmol, 186.2 mg), CuI (0.4 mmol, 76.8 mg), 1,10-phenanthroline (0.05 mmol, 9.4 mg) and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.4 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A colorless liquid (60.5 mg, 48%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.86 (d, J = 7.9 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.38 (td, J = 7.6, 1.2 Hz, 1H), 7.34 (td, J = 7.6, 1.3 Hz, 1H), 7.04 (s, 1H), 6.98 (s, 2H), 2.35 (s, 3H), 2.19 (s, 6H). 13 13C NMR (126 MHz, CDCl3): δ 142.47, 140.69, 140.33, 138.18, 137.94, 130.88, 128.11, 124.07, 123.76, 123.31, 123.07, 122.14, 21.10, 20.59. HRMS (EI) m / z calcd for C 17 H 16 S [M] + : 252.0973, found 252.0965.

[0090] Example 13

[0091]

[0092] 1.0 equivalent of 2,6 - di - tert - butylpyridine - derived dibenzothiophenium salt (0.2 mmol, 104.8 mg), 1.5 equivalents of 2 - triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10 - phenanthroline (0.02 mmol, 3.8 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N - dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (28.7 mg, 76%) was obtained by flash column chromatography. 1 HNMR(500MHz,CDCl3):δ7.83(d,J = 7.9Hz,1H),7.77(d,J = 7.9Hz,1H),7.47(d,J = 7.9Hz,1H),7.39(t,J = 7.4Hz,1H),7.35(t,J = 7.5Hz,1H),7.17(s,1H),7.15(d,J = 7.9Hz,1H),1.40(s,9H),1.35(s,9H). 13 C NMR(126MHz,CDCl3):δ167.25,164.49,144.04,141.44,140.16,139.50,125.12,124.50,124.44,124.15,123.38,121.87,114.84,40.50,37.74,31.24,30.05.HRMS(EI)m / z calcd for C 21 H 25 NS[M] + :323.1708,found 323.1702.

[0093] Example 14

[0094]

[0095] 1.0 equivalent of thiophene-derived dibenzothiophenium salt (0.2 mmol, 83.5 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvents were removed under reduced pressure. A white solid (13.0 mg, 30%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.79 (d, J = 7.8 Hz, 1H), 7.73 (d, J = 7.8 Hz, 1H), 7.41 (s, 1H), 7.38–7.28 (m, 4H), 7.07 (t, 1H). 13 C NMR (126 MHz, CDCl3): δ 140.32, 139.04, 137.38, 137.21, 127.91, 125.46, 125.04, 124.63, 124.43, 123.38, 122.10, 119.69.

[0096] Example 15

[0097]

[0098] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.5 mmol, 212.3 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.75 mmol, 186.3 mg), CuI (0.4 mmol, 76.7 mg), 1,10-phenanthroline (0.05 mmol, 9.6 mg) and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.0 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvents were removed under reduced pressure. A white solid (82.2 mg, 74%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.50 (d, J = 8.1 Hz, 2H), 7.23–7.16 (m, 5H), 7.13 (d, J = 3.8 Hz, 1H), 7.03 (dd, J = 5.0, 3.6 Hz, 1H), 2.37 (s, 3H). 1313C NMR (126 MHz, CDCl3): δ 144.37, 140.75, 139.30, 138.24, 131.47, 129.60, 126.34, 124.42, 124.09, 123.38, 122.20, 118.81, 21.22.

[0099] Example 16

[0100]

[0101] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.5 mmol, 212.3 mg), 1.5 equivalents of 2-triethylsilylbenzofuran (0.75 mmol, 174.3 mg), CuI (0.4 mmol, 76.7 mg), 1,10-phenanthroline (0.05 mmol, 9.5 mg) and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.3 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (98.8 mg, 95%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CD3CN): δ 7.79 (d, J = 8.2 Hz, 2H), 7.62 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.34–7.28 (m, 3H), 7.25 (td, J = 7.5, 0.9 Hz, 1H), 7.13 (s, 1H), 2.38 (s, 3H). 13 13C NMR (126 MHz, CDCl3): δ 156.17, 154.75, 138.57, 129.47, 129.33, 127.74, 124.87, 123.97, 122.83, 120.71, 111.07, 100.53, 21.37.

[0102] Example 17

[0103]

[0104] 1.0 equivalent of toluene-derived dibenzothiophene sulfonium salt (0.5 mmol, 212.4 mg), 1.5 equivalents of 2,2'-bithiophene-5-triethylsilane (0.75 mmol, 210.3 mg), CuI (0.4 mmol, 76.7 mg), 1,10-phenanthroline (0.05 mmol, 9.4 mg) and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.2 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A yellow solid (96.2 mg, 75%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.50 (d, J = 8.1 Hz, 2H), 7.23–7.17 (m, 5H), 7.13 (d, J = 3.8 Hz, 1H), 7.03 (dd, J = 5.0, 3.6 Hz, 1H), 2.37 (s, 3H). 13 13C NMR (126 MHz, CDCl3): δ 143.32, 137.53, 137.51, 136.12, 131.28, 129.59, 127.81, 125.51, 124.54, 124.21, 123.46, 123.16, 21.18.

[0105] Example 18

[0106]

[0107] 1.0 equivalent of toluene-derived dibenzothiophene sulfonium salt (0.2 mmol, 85.3 mg), 1.5 equivalents of 2-triethylsilyl-5-phenylthiophene (0.3 mmol, 82.6 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (32.1 mg, 64%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.65–7.62 (m, 2H), 7.53 (d, J = 8.0 Hz, 2H), 7.39 (t, J = 7.7 Hz, 2H), 7.31–7.24 (m, 3H), 7.20 (d, J = 8.1 Hz, 2H), 2.38 (s, 3H). 1313C NMR (126 MHz, CDCl3): δ 143.79, 143.00, 137.39, 134.37, 131.52, 129.56, 128.87, 127.36, 125.55, 125.51, 123.91, 123.45, 21.18.

[0108] Example 19

[0109]

[0110] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.3 mg), 1.5 equivalents of 2-triethylsilyl-5-pyridylthiophene (0.3 mmol, 83.1 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.9 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (35.7 mg, 71%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 8.58 (d, J = 4.8 Hz, 1H), 7.71–7.65 (m, 2H), 7.57 (d, J = 7.9 Hz, 3H), 7.29 (d, J = 3.8 Hz, 1H), 7.21 (d, J = 7.9 Hz, 2H), 7.17–7.12 (m, 1H), 2.38 (s, 3H). 13 13C NMR (126 MHz, CDCl3): δ 152.38, 149.33, 146.55, 142.87, 137.84, 136.79, 131.39, 129.62, 125.85, 125.64, 123.52, 121.73, 118.56, 21.22.

[0111] Example 20

[0112]

[0113] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.2 mg), 1.5 equivalents of 2-triethylsilylthiophene (0.3 mmol, 59.6 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (21.6 mg, 62%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.52 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 3.6 Hz, 1H), 7.25 (d, J = 6.1 Hz, 1H), 7.20 (d, J = 7.9 Hz, 2H), 7.11–7.05 (m, 1H), 2.38 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 144.55, 137.30, 131.62, 129.52, 127.89, 125.84, 124.24, 122.54, 21.15.

[0114] Example 21

[0115]

[0116] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.5 mmol, 212.4 mg), 1.5 equivalents of 2-triethylsilylselenophene (0.75 mmol, 184.7 mg), CuI (0.4 mmol, 76.8 mg), 1,10-phenanthroline (0.05 mmol, 9.5 mg), and 1.5 equivalents of cesium fluoride (0.75 mmol, 114.3 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (1.0 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A green solid (69.7 mg, 63%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.90 (dd, J = 5.6, 0.9 Hz, 1H), 7.46 (d, J = 8.1 Hz, 2H), 7.42 (dd, J = 3.7, 0.8 Hz, 1H), 7.30 (dd, J = 5.6, 3.8 Hz, 1H), 7.17 (d, J = 7.9 Hz, 2H), 2.36 (s, 3H). 1313C NMR (126 MHz, CDCl3): δ 150.96, 137.42, 133.63, 130.52, 129.54, 129.35, 126.26, 124.66, 21.14。

[0117] Example 22

[0118]

[0119] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.2 mg), 1.5 equivalents of 2-triethylsilyl-5-methylbenzothiophene (0.3 mmol, 79.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.7 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (36.7 mg, 77%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.69 (d, J = 8.2 Hz, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.55 (s, 1H), 7.43 (s, 1H), 7.23 (d, J = 7.7 Hz, 2H), 7.13 (d, J = 8.2 Hz, 1H), 2.46 (s, 3H), 2.39 (s, 3H). 13 13C NMR (126 MHz, CDCl3): δ 144.46, 141.08, 138.12, 136.48, 134.11, 129.56, 126.28, 125.85, 123.37, 121.83, 118.55, 21.40, 21.22。

[0120] Example 23

[0121]

[0122] 1.0 equivalent of toluene-derived dibenzothiophene sulfonium salt (0.2 mmol, 85.2 mg), 1.5 equivalents of 2-triethylsilyl-5-methoxybenzothiophene (0.3 mmol, 83.9 mg), CuI (0.16 mmol, 30.7 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (43.7 mg, 86%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.68 (d, J = 8.7 Hz, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.43 (s, 1H), 7.23 (d, J = 8.2 Hz, 3H), 6.96 (dd, J = 8.7, 2.2 Hz, 1H), 3.88 (s, 3H), 2.39 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 157.62, 145.64, 141.75, 138.22, 131.72, 131.58, 129.58, 126.25, 122.86, 118.69, 114.24, 105.60, 55.50, 21.22.

[0123] Example 24

[0124]

[0125] 1.0 equivalent of toluene-derived dibenzothiophene sulfonium salt (0.2 mmol, 85.1 mg), 1.5 equivalents of 2-triethylsilyl-5-chlorobenzothiophene (0.3 mmol, 85.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.9 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (12.9 mg, 25%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.72 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 7.9 Hz, 2H), 7.42 (s, 1H), 7.24 (d, J = 7.9 Hz, 3H), 2.40 (s, 3H). 1313C NMR (126 MHz, CDCl3): δ 146.52, 141.86, 138.76, 137.37, 131.03, 130.63, 129.69, 126.41, 124.47, 123.20, 122.84, 118.02, 21.27。

[0126] Example 25

[0127]

[0128] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.1 mg), 1.5 equivalents of 2-triethylsilyl-3-methoxythiophene (0.3 mmol, 68.8 mg), CuI (0.16 mmol, 30.7 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A yellow liquid (30.5 mg, 75%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.62 (d, J = 7.9 Hz, 2H), 7.18 (d, J = 7.8 Hz, 2H), 7.12 (d, J = 5.5 Hz, 1H), 6.93 (d, J = 5.5 Hz, 1H), 3.90 (s, 3H), 2.35 (s, 3H). 13 13C NMR (126 MHz, CDCl3): δ 153.30, 136.13, 130.47, 129.18, 126.83, 121.57, 120.37, 117.47, 58.74, 21.16. HRMS (EI) m / z calcd for C 12 H 12 OS [M] + : 204.0609, found 204.0602.

[0129] Example 26

[0130]

[0131] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.1 mg), 1.5 equivalents of 2-triethylsilyl-5-methylthiophene (0.3 mmol, 63.9 mg), CuI (0.16 mmol, 30.9 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (20.9 mg, 55%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.45 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 7.06 (d, J = 3.4 Hz, 1H), 6.72 (d, J = 2.6 Hz, 1H), 2.51 (s, 3H), 2.36 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 142.09, 138.90, 136.78, 131.90, 129.44, 126.05, 125.38, 122.31, 21.12, 15.44. HRMS (EI) m / z calcd for C 12 H 12 S [M] + : 188.0660, found 188.0652.

[0132] Example 27

[0133]

[0134] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.3 mg), 1.5 equivalents of 2-triethylsilyl-5-methylthiophenyl (0.3 mmol, 73.8 mg), CuI (0.16 mmol, 30.9 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (29.9 mg, 68%) was obtained by flash column chromatography. 1HNMR(500MHz,CDCl3):δ7.44(d,J=7.8Hz,2H),7.18(d,J=7.9Hz,2H),7.11(d,J=3.7Hz,1H),7.04(d,J=3.7Hz,1H),2.52(s,3H),2.36(s,3H). 13 C NMR(126MHz,CDCl3):δ146.85,137.56,135.82,132.16,131.29,129.56,125.51,122.70,22.25,21.16.HRMS(EI)m / zcalcd for C 12 H 12 S2[M] + :220.0380,found 220.0374.

[0135] Example 28

[0136]

[0137] 1.0 equiv of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.2 mg), 1.5 equiv of 5-triethylsilyl-5'-hexyl-2,2'-bithiophene (0.3 mmol, 109.6 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equiv of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 h, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A yellow solid (31.4 mg, 46%) was obtained by flash column chromatography. 1 HNMR(500MHz,CDCl3):δ7.48(d,J=8.2Hz,2H),7.18(d,J=8.0Hz,2H),7.15(d,J=3.7Hz,1H),7.05(d,J=3.7Hz,1H),6.99(d,J=3.5Hz,1H),6.68(d,J=3.5Hz,1H),2.80(t,J=7.6Hz,2H),2.37(s,3H),1.69(p,J=7.5Hz,2H),1.44–1.27(m,6H),0.90(t,J=5Hz,3H). 13CNMR(126MHz, CDCl3): δ145.32, 142.61, 137.31, 136.75, 134.87, 131.42, 129.55, 125.44, 124.74, 123.75, 123.13, 123.09, 31.56, 30.18, 28.75, 22.57, 21.17, 14.07. HRMS(EI) m / z calcd for C 21 H 24 S2[M] + : 340.1319, found 340.1308.

[0138] Example 29

[0139]

[0140] 1.0 equivalent of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.2 mg), 1.5 equivalents of 2-triethylsilyl-3,4-dimethoxythiophene (0.3 mmol, 77.8 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 4.0 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After purging with nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 h, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvents were removed under reduced pressure. A yellow liquid (30.1 mg, 64%) was obtained by flash column chromatography. 1 HNMR(500MHz, CDCl3): δ7.59(d, J = 8.2Hz, 2H), 7.19(d, J = 8.0Hz, 2H), 6.12(s, 1H), 3.87(s, 3H), 3.80(s, 3H), 2.36(s, 3H). 13 C NMR(126MHz, CDCl3): δ151.29, 143.05, 137.12, 130.28, 129.29, 126.80, 125.73, 93.60, 60.30, 57.15, 21.21. HRMS(EI) m / z calcd for C 13 H 14 O2S[M] + : 234.0715, found 234.0707.

[0141] Example 30

[0142]

[0143] 2.0 equivalents of toluene-derived dibenzothiophenium salt (0.2 mmol, 85.0 mg), 1.0 equivalent of (4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(triethylsilane) (0.1 mmol, 80.9 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 3.0 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvents were removed under reduced pressure. A yellow solid (22.2 mg, 30%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.79 (s, 2H), 7.60 (d, J = 8.1 Hz, 4H), 7.34 (d, J = 3.4 Hz, 2H), 7.20 (d, J = 8.0 Hz, 4H), 6.93 (d, J = 3.4 Hz, 2H), 2.95–2.84 (m, 4H), 2.38 (s, 6H), 1.72 (hept, J = 6.1 Hz, 2H), 1.50–1.33 (m, 16H), 0.96 (m, 12H). 13 C NMR (126 MHz, CDCl3): δ 145.76, 144.71, 138.67, 138.31, 137.49, 137.21, 131.53, 129.52, 127.71, 126.31, 125.39, 123.48, 118.29, 41.48, 34.34, 32.52, 28.95, 25.82, 23.05, 21.26, 14.17, 10.95. HRMS (EI) m / z calcd for C 48 H 54 S4 [M] + : 758.3108, found 758.3101.

[0144] Application 1: Post-modification of drugs

[0145] Example 1: Post-modification of etofenprox

[0146]

[0147] 1.0 equivalent of etofenprox-derived dibenzothiophene sulfonium salt (0.2 mmol, 141.9 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.9 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A yellow liquid (50.3 mg, 50%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.84 (d, J = 7.8 Hz, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.75 (s, 2H), 7.36–7.29 (m, 5H), 7.27 (d, J = 5.0 Hz, 1H), 7.11 (t, J = 7.4 Hz, 1H), 7.03 (t, J = 7.7 Hz, 3H), 6.99 (s, 1H), 6.92 (dd, J = 8.2, 3.0 Hz, 2H), 4.50 (s, 2H), 4.17 (q, J = 6.9 Hz, 2H), 3.50 (s, 2H), 1.55 (t, J = 6.9 Hz, 3H), 1.40 (s, 6H). 13 C NMR (126 MHz, CDCl3): δ 157.31, 157.11, 153.80, 140.86, 140.77, 140.05, 139.90, 139.78, 129.68, 129.55, 127.35, 126.91, 123.98, 123.84, 123.31, 123.20, 122.58, 122.02, 121.78, 118.93, 117.65, 117.59, 113.89, 112.25, 80.12, 72.77, 64.48, 38.59, 26.15, 14.93. HRMS (EI) m / z calcd for C 33 H 32 O3S [M] + : 508.2072, found 508.2057.

[0148] Example 2: Post-modification of Clofibrate

[0149]

[0150] 1.0 equivalent of clofibrate-derived dibenzothiophenium salt (0.2 mmol, 115.3 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.8 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.9 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 h, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A yellow liquid (45.3 mg, 60%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.84 (d, J = 7.6 Hz, 1H), 7.79 (d, J = 7.9 Hz, 1H), 7.71 (s, 1H), 7.69–7.67 (m, 1H), 7.35 (q, J = 8.0, 7.6 Hz, 2H), 7.16 (ddd, J = 8.8, 2.5, 0.8 Hz, 1H), 6.80–6.75 (m, 1H), 4.25 (q, J = 7.0 Hz, 2H), 1.66 (s, 6H), 1.35–1.07 (m, 3H). 13 C NMR (126 MHz, CDCl3): δ 173.86, 150.93, 140.32, 139.58, 138.70, 129.53, 128.13, 127.80, 127.27, 124.42, 124.26, 123.59, 123.23, 121.89, 118.84, 80.87, 61.65, 25.21, 14.06. HRMS (EI) m / z calcd for C 20 H 19 ClO3S [M] + : 374.0743, found 374.0731.

[0151] Example 3: Post-modification of Fenofibrate

[0152]

[0153] 1.0 equivalent of fenofibrate-derived dibenzothiophenium salt (0.2 mmol, 138.8 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.7 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.9 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A yellow solid (42.8 mg, 45%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 8.19 (d, J = 2.0 Hz, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.80 (d, J = 7.3 Hz, 1H), 7.76 (d, J = 8.4 Hz, 2H), 7.73 (s, 1H), 7.68 (dd, J = 8.6, 2.0 Hz, 1H), 7.48 (d, J = 8.4 Hz, 2H), 7.39–7.29 (m, 2H), 6.84 (d, J = 8.7 Hz, 1H), 5.11 (p, J = 6.3 Hz, 1H), 1.78 (s, 6H), 1.22 (d, J = 6.2 Hz, 6H). 13 C NMR (126 MHz, CDCl3): δ 193.96, 172.86, 156.04, 140.24, 139.55, 138.94, 138.64, 136.09, 132.25, 131.22, 130.71, 130.39, 128.67, 125.24, 124.42, 124.26, 123.59, 123.13, 121.86, 115.55, 80.88, 69.51, 25.40, 21.52. HRMS (EI) m / z calcd for C 28 H 25 ClO4S [M] + : 492.1162, found 492.1154.

[0154] Example 4: Post-modification of Gemfibrozil methyl ester

[0155]

[0156] 1.0 equivalent of Gemfibrozil methyl ester-derived dibenzothiophene sulfonium salt (0.2 mmol, 119.5 mg), 1.5 equivalents of 2-triethylsilylbenzothiophene (0.3 mmol, 74.0 mg), CuI (0.16 mmol, 30.9 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg), and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 14 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (49.5 mg, 63%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.82 (d, J = 7.9 Hz, 1H), 7.76 (d, J = 7.8 Hz, 1H), 7.35 (t, J = 7.4 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H), 7.25 (s, 1H), 7.18 (s, 1H), 6.70 (s, 1H), 3.98 (t, J = 5.6 Hz, 2H), 3.68 (s, 3H), 2.43 (s, 3H), 2.22 (s, 3H), 1.80–1.71 (m, 4H), 1.24 (s, 6H). 13 C NMR (126 MHz, CDCl3): δ 178.27, 157.01, 143.79, 140.30, 139.86, 134.85, 132.74, 125.71, 124.27, 124.18, 123.74, 123.20, 122.35, 121.92, 113.08, 68.06, 51.75, 42.08, 37.05, 25.18, 25.13, 21.09, 15.63. HRMS (EI) m / z calcd for C 24 H 28 O3S [M] + : 396.1759, found 396.1746.

[0157] Application 2: Asymmetric cross-coupling reaction

[0158] Example 1:

[0159]

[0160] Step 1: Suzuki cross-coupling reaction

[0161]

[0162] 1.0 equivalent of 2-bromothiophene (2.0 mmol, 333.3 mg), 1.2 equivalents of 2-triethylsilyl-7-pinacol benzo[b]thiophene (2.4 mmol, 899.5 mg), Pd(PPh3)4 (0.1 mmol, 117.5 mg) and 2.4 equivalents of potassium carbonate (4.8 mmol, 670.5 mg) were placed in a reaction flask. After purging with nitrogen three times, dry 1,4-dioxane (8.0 mL) and water (2.0 mL) were added. After stirring at 110 °C for 12 h, the reaction was quenched by adding saturated sodium carbonate solution to the reaction system. Then the organic phase was extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and then the organic solvent was removed under reduced pressure. A colorless liquid (639.6 mg, 97%) was obtained by flash column chromatography. 1 H NMR (500 MHz, CDCl3): δ 7.79 (d, J = 7.9 Hz, 1H), 7.66 (d, J = 3.1 Hz, 1H), 7.55 (d, J = 6.8 Hz, 2H), 7.40 (dd, J = 9.0, 6.3 Hz, 2H), 7.23–7.17 (m, 1H), 1.05 (t, J = 7.7 Hz, 9H), 0.90 (q, J = 7.6 Hz, 6H). 13 C NMR (126 MHz, CDCl3): δ 142.88, 142.10, 141.39, 139.29, 132.11, 129.23, 127.70, 125.36, 125.13, 124.54, 123.61, 122.70, 7.37, 4.20. HRMS (EI) m / z calcd for C 18 H 22 S2Si [M] + : 330.0932, found 330.0929.

[0163] Step 2: Hiyama cross-coupling reaction

[0164]

[0165] 1.0 equivalent of benzene-derived dibenzothiophenium salt (0.2 mmol, 82.3 mg), 1.5 equivalents of 2-triethylsilyl-7-thienylbenzothiophene (0.3 mmol, 98.9 mg), CuI (0.16 mmol, 30.8 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.8 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 17 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (44.3 mg, 76%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.75 (t, J = 7.7 Hz, 3H), 7.65 (d, J = 3.4 Hz, 1H), 7.62 (s, 1H), 7.54 (d, J = 7.4 Hz, 1H), 7.47–7.39 (m, 4H), 7.36 (t, J = 7.4 Hz, 1H), 7.24–7.18 (m, 1H). 13 C NMR (126 MHz, CDCl3): δ 144.50, 142.48, 141.71, 137.31, 134.01, 129.31, 128.94, 128.36, 127.73, 126.47, 125.36, 125.32, 125.08, 123.98, 122.88, 119.82. HRMS (EI) m / z calcd for C 18 H 12 S2 [M] + : 292.0380, found 292.0375.

[0166] Example 2:

[0167]

[0168] Step 1: Suzuki cross-coupling reaction

[0169]

[0170] 1.0 equivalent of 1-bromo-4-methoxybenzene (1.0 mmol, 189.1 mg), 1.2 equivalents of 2-triethylsilyl-7-pinacol benzo[b]thiophene (1.2 mmol, 449.5 mg), Pd(PPh3)4 (0.05 mmol, 58.8 mg) and 2.4 equivalents of potassium carbonate (2.4 mmol, 335.3 mg) were placed in a reaction flask. After displacing nitrogen three times, dry 1,4-dioxane (4.0 mL) and water (1.0 mL) were added. After stirring at 110 °C for 12 hours, the reaction was quenched by adding saturated sodium carbonate solution to the reaction system. Then the organic phase was extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and then the organic solvent was removed under reduced pressure. A colorless liquid (336.9 mg, 95%) was obtained by flash column chromatography. 1 1H NMR (500 MHz, CDCl3): δ 7.78 (d, J = 7.5 Hz, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.54 (s, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.32 (d, J = 6.9 Hz, 1H), 7.05 (d, J = 8.7 Hz, 2H), 3.89 (s, 3H), 1.02 (t, J = 7.8 Hz, 9H), 0.86 (q, J = 7.9 Hz, 6H). 13 13C NMR (126 MHz, CDCl3): δ 159.26, 142.59, 141.72, 139.02, 136.09, 133.33, 132.11, 129.35, 124.68, 123.74, 121.98, 114.07, 55.30, 7.36, 4.18. HRMS (EI) m / z calcd for C 21 H 26 OSSi[M] + : 354.1474, found 354.1462.

[0171] Step 2: Hiyama cross-coupling reaction

[0172]

[0173] 1.0 equivalent of benzene-derived dibenzothiophenium salt (0.2 mmol, 82.3 mg), 1.5 equivalents of 2-triethylsilyl-7-(4-methoxyphenyl)benzothiophene (0.3 mmol, 106.6 mg), CuI (0.16 mmol, 30.9 mg), 1,10-phenanthroline (0.02 mmol, 3.9 mg) and 1.5 equivalents of cesium fluoride (0.3 mmol, 45.9 mg) were placed in a reaction flask. After displacing nitrogen three times, dry N,N-dimethylformamide (0.4 mL) was added. After stirring at 70 °C for 17 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A white solid (37.9 mg, 60%) was obtained by flash column chromatography. 1 HNMR (500 MHz, CDCl3): δ 7.75 - 7.71 (m, 5H), 7.63 (s, 1H), 7.46 - 7.41 (m, 3H), 7.36 - 7.32 (m, 2H), 7.07 (d, J = 8.5 Hz, 2H), 3.90 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 159.36, 144.35, 141.36, 138.51, 136.23, 134.22, 133.00, 129.29, 128.90, 128.22, 126.40, 125.22, 124.10, 122.17, 119.85, 114.14, 55.33. HRMS (EI) m / z calcd for C 21 H 16 OS[M] + : 316.0922, found 316.0911.

[0174] Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will understand that: within the spirit and scope of the present invention and the appended claims, various substitutions, changes, and modifications are possible. Therefore, the scope of the present invention is not limited to the content disclosed in the embodiments.

Claims

1. A synthetic method for constructing a new C-C bond through the cross-coupling reaction of copper-catalyzed aryl sulfonium salts and arylsilanes, characterized in that: The method uses aryl sulfonium salts and aryl silanes as reaction raw materials, with aryl sulfonium salts as electrophiles and aryl silanes as nucleophiles, to synthesize biaryl compounds under the conditions of a catalyst / ligand / base / solvent; wherein, the catalyst is cuprous iodide, and 1,10-phenanthroline (i.e., 1,10-Phen) and cesium fluoride are used as additives to achieve the synthesis of biaryl compounds at 70 °C. The reaction general formula of the method is as follows: Among them, Ar1 and Ar2 represent the same or different aryl systems; The aryl sulfonium salt is any one of the following compounds: Among them, R, R1, and R2 are straight-chain alkyl groups with 1-15 carbon atoms, branched-chain alkyl groups with 3-15 carbon atoms, or cycloalkyl groups with 3-8 carbon atoms; The aryl silane is any one of the following compounds: Among them, R is a straight-chain alkyl group with 1-15 carbon atoms, a branched-chain alkyl group with 3-15 carbon atoms, or a cycloalkyl group with 3-8 carbon atoms.

2. The synthesis method according to claim 1, characterized in that: The straight-chain alkyl groups with 1-15 carbon atoms include: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; the branched-chain alkyl groups with 3-15 carbon atoms include: isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl; the cycloalkyl groups with 3-8 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

3. The synthesis method according to claim 1, wherein: The straight-chain alkyl groups with 1-15 carbon atoms include: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; the branched-chain alkyl groups with 3-15 carbon atoms include: isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl; the cycloalkyl groups with 3-8 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

4. The synthesis method according to any one of claims 1 to 3, characterized in that: The method includes the following steps: (1) Under the protection of inert gas, in the presence of CuI as a catalyst, 1,10-Phen and cesium fluoride are added as additives, and the arylsulfonium salt and arylsilane are placed in N,N-dimethylformamide for reaction to obtain a mixture; (2) Dichloromethane and silica gel powder are added to the reaction system, then the organic solvent is removed under reduced pressure, and finally a pure product is obtained by a flash column chromatography machine.

5. The synthesis method according to claim 4, characterized in that: (2) The method comprises the following steps: 1.0 equivalent of arylsulfonium salt, 1.5 equivalents of arylsilane, CuI, 1,10-Phen, and 1.5 equivalents of cesium fluoride are placed in a reaction flask. The addition amount of CuI is 80.0 mol% of the total molar amount of arylsulfonium salt, and the addition amount of 1,10-Phen is 10.0 mol% of the total molar amount of arylsulfonium salt; after displacing nitrogen three times, dry N,N-dimethylformamide is added to make the concentration of the solution, that is, the concentration of arylsulfonium salt in N,N-dimethylformamide, remain at 0.5 M; after stirring at 70 °C for 14 hours, dichloromethane and silica gel powder are added to the reaction system, then the organic solvent is removed under reduced pressure, and finally a pure product is obtained by a flash column chromatography machine.

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