Method for generating carbocations by photocatalysis of thiol compound and carrying out coupling reaction with nucleophilic reagent

Abstract

The invention provides a method for generating carbocations through photocatalysis of a thiol compound and carrying out a coupling reaction with a nucleophilic reagent. The method comprises the following steps: adding a photocatalyst, a thiol compound and a nucleophilic reagent into an organic solvent to obtain a solution A; in an oxygen-containing environment, the solution A is irradiated by a light source, under the action of a photocatalyst, the thiol compound is desulfurized to generate carbocations, and then the carbocations and a nucleophilic reagent are subjected to a coupling reaction; the method is mild in reaction condition and can be realized at room temperature in an air atmosphere, and the whole process is simple, efficient, green and economical.

Description

Technical Field

[0001] The present invention belongs to the technical field of generating carbocations and performing coupling reactions, and specifically includes a method for photocatalytically generating carbocations from thiol compounds and performing coupling reactions with nucleophiles. Background Art

[0002] As an important reactive intermediate, carbocations have extensive applications in organic reactions. The traditional method for generating carbocations is that alkyl electrophiles lose two electrons simultaneously under Lewis acid conditions to form carbocations. Or starting from substrate alkenes, carbocations are generated under the action of strong Brønsted acids. However, due to the required strong acidic conditions, the functional group compatibility is limited. Visible-light photocatalyzed redox reactions have developed into a powerful synthetic method, enabling the synthesis of various complex organic compounds from simple starting materials under mild conditions. The strategy for generating carbocations via visible-light photocatalysis mainly relies on the generation of carbon radicals from carbocation precursors through single-electron transfer, and then the carbon radicals further undergo single-electron oxidation to generate carbocations. However, this strategy has the following problems: 1. The carbon radicals generated by photoredox catalysis have the characteristics of short lifespan and low concentration, making it difficult to further undergo the second single-electron oxidation to generate carbocations; 2. Carbon radicals are prone to radical reactions. To solve this problem, a method of stabilizing and oxidizing carbon radicals by metal copper oxidants to generate carbocations has been reported in recent years (Angew. Chem. Int. Ed. 2020, 59, 197 - 202; Org. Lett. 2022, 24, 2679 - 2683; Org. Biomol. Chem., 2024, 22, 25 - 36). However, this method has the problem of heavy metal residues, which restricts its potential applications, especially in the development and late-stage modification of drug molecules. In 2016, the Knowles group reported that the cation radical obtained after single-electron oxidation of TEMPO-derived alkoxyamine substrates was further cleaved to obtain carbocation intermediates (Angew. Chem. Int. Ed. 2016, 55, 9969 - 9973). However, this substrate needs to be further synthesized, and this method is not applicable to the generation of primary carbocations. In recent years, the polarity inversion strategy has been applied to the field of carbocation synthesis. Using redox-active esters in situ generated from carboxylic acids or benzyl C-H bond substrates, carbon radicals are obtained through single-electron reduction or hydrogen atom transfer processes, and then the carbon radicals are oxidized by the reduced photocatalyst to generate carbocations for subsequent reactions (J. Am. Chem. Soc. 2020, 142, 1211 - 1216; Nature Commun. 2023, 14, 6856; J. Am. Chem. Soc. 2020, 142, 9493 - 9500; J. Am. Chem. Soc. 2023, 145, 3861 - 3868). In 2022, the Yoon group used an equivalent amount of copper salt to stabilize and oxidize the generated carbon radicals to form carbocations for decarboxylative coupling reactions (Nat. Chem. 2022, 14, 94 - 99).

[0003] The key to the success of these photocatalytic reactions for generating carbocations lies in the stabilization of the generated carbon radical intermediates by metal salts or reduced photocatalysts and the subsequent single-electron oxidation in the second step to obtain carbocations. Therefore, it is of great significance to develop a novel, mild and efficient method for generating carbocations and then coupling with various nucleophiles. SUMMARY OF THE INVENTION

[0004] Aiming at the above problems existing in the prior art, the purpose of the present invention is to provide a method for photocatalytically generating carbocations from thiol compounds and coupling with nucleophiles. This method can directly desulfurize thiol compounds to generate carbocations under photocatalytic conditions, and then the carbocations can couple with various nucleophiles to complete the construction of C-C bonds or other C-heteroatom bonds (C-N bonds, C-O bonds, C-S bonds). The whole process is simple, efficient, green and economical.

[0005] To achieve the above purpose, the technical solutions adopted by the present invention include:

[0006] The present invention discloses a method for photocatalytically generating carbocations from thiol compounds and coupling with nucleophiles, and the method includes the following steps:

[0007] Add a photocatalyst, a thiol compound, and a nucleophile to an organic solvent to obtain solution A;

[0008] In an oxygen-containing environment, irradiate solution A with a light source. Under the action of the photocatalyst, the thiol compound desulfurizes to generate a carbocation, and then the carbocation couples with the nucleophile.

[0009] Further, the thiol compound is selected from the compounds having the structure shown in formula I:

[0010]

[0011] Wherein, R1, R2, and R3 are each independently selected from any one of H, C1-C 20 alkyl, aryl, C1-C 12 alkoxy, COO t Bu, allyl, F, Cl, Br.

[0012] The present invention realizes the coupling reaction between thiol compounds and nucleophiles for the first time under photocatalytic conditions, and efficiently converts the C-S bond in thiol compounds into C-C (such as arylindole compounds) or other C-hetero bonds (C-N bond, such as arylsulfonamide compounds; C-O bond, such as arylalkyl ethers, arylalkyl alcohols, aryl esters; C-S bond, such as aryl sulfides). The specific process of this coupling reaction is as follows: under visible light irradiation, the thiol compound is oxidized by the excited photocatalyst to obtain a sulfur radical and a reduced photocatalyst. Oxygen in the oxygen-containing environment returns the reduced photocatalyst to the ground state. The sulfur radical dimerizes to obtain a disulfide compound, and the disulfide compound is oxidized by the excited photocatalyst to a disulfide compound cation radical. The disulfide radical cation undergoes heterolytic cleavage of the C-S bond to obtain a carbocation, a carbon radical and a by-product S8. The carbon radical couples with the sulfur radical to obtain a thioether. The thioether can also undergo heterolytic cleavage to generate a carbocation and a sulfur radical. Finally, the obtained carbocation undergoes a coupling reaction with various nucleophiles to obtain the desired product.

[0013] Further, the aryl is selected from any one of substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, and the substituent is selected from any one of alkyl, alkoxy, F, Cl, and Br.

[0014] Further, the thiol compounds are selected from one or more of 1-phenylethanethiol, 1-adamantanethiol, 1-(naphthalen-2-yl)ethane-1-thiol, 1-(4-fluorophenyl)ethane-1-thiol, 1-(2-methylphenyl)ethane-1-thiol, 1-(3-methylphenyl)ethane-1-thiol, 1-(4-methylphenyl)ethane-1-thiol, 1-(4-chloro)phenylethanethiol, 1-([1,1'-biphenyl]-4-yl)ethane-1-thiol, 1,2,3,4-tetrahydronaphthalene-1-thiol, 1-(benzo[d][1,3]dioxol-5-yl)ethane-1-thiol, diphenylmethanethiol, tert-butylthiol, 4-methoxybenzylthiol, 4-tert-butylbenzylthiol, and 1-naphthalenemethanethiol.

[0015] Further, the nucleophile is selected from the structures shown in any one of the following formulas II-1 to II-8:

[0016]

[0017] In formula II-1, R4 and R5 are each independently selected from any one of H, alkyl, aryl, and alkoxy;

[0018] In formula II-2, R6, R7, and R8 are each independently selected from any one of H, OMe, t Bu, i Pr, Et, and Me;

[0019] In formula II-3, R9 is selected from any one of H, alkyl, aryl, and alkoxy;

[0020] In formula II-4, R 10 is selected from any one of H, alkyl, aryl, and alkoxy;

[0021] In formula II-5, R 11 is selected from H or alkyl;

[0022] In formula II-6, R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from any one of H, aryl, alkoxy, alkyl, methanol group, allyl, and Cl;

[0023] In formula II-7, R 19 and R 20 are each independently selected from any one of H, CHO, COMe, COOMe, and COOEt, and X1 and X2 are each independently selected from N or C;

[0024] In formula II-8, R 21 is selected from alkyl or aryl.

[0025] Furthermore, the nucleophile is selected from one or more of p-toluenesulfonamide, 4-fluorobenzenesulfonamide, p-cyanobenzenesulfonamide, cyclopropanesulfonamide, thiophene-2-sulfonamide, naphthalene-1-sulfonamide, N-methylbenzenesulfonamide, 4-hydroxybenzenesulfonamide, p-toluenesulfonamide, 3,5-difluorobenzenesulfonamide, benzenesulfonamide, benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-fluorobenzoic acid, phenylacetic acid, water, anisole, p-tert-butylbenzenethiol, N-(p-toluenesulfonyl)indole, valproic acid, probenecid, celecoxib, and aspirin. It has been found through experiments that for drug molecules such as valproic acid, probenecid, celecoxib, and aspirin, they can also undergo a coupling reaction with thiol compounds to obtain new compound molecules. Therefore, this method has potential application value in the modification of drug molecules.

[0026] The photocatalyst in the present invention can catalyze and cycle this reaction process as long as its oxidation potential is appropriate. Those skilled in the art are capable of selecting a suitable photocatalyst, and the present invention does not make specific limitations in this regard. Exemplarily, the photocatalyst is selected from 9-mesityl-10-phenylacridin-10-ium tetrafluoroborate (Mes-Acr-Ph + BF4 - ), 9-mesityl-10-methylacridinium perchlorate (Acr + -Mes ClO4- ) one or more of 2,4,5,6-tetrakis(9-carbazolyl)isophthalonitrile (4CzIPN), 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPAIPN), eosin Y, rhodamine 6G (Rh 6G), anthraquinone (AQ), fluorescein, bis[2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine][2-2'-bi(4-tert-butylpyridine)]iridium bis(hexafluorophosphate) (Ir[dF(CF3)ppy]2(dtbpy)PF6), tris(2-phenylpyridine)iridium (Ir(ppy)3), and (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2-pyridyl)phenyl]iridium(III) hexafluorophosphate ([Ir(dtbbpy)(ppy)2]PF6).

[0027] The organic solvent in the present invention only provides a solution environment for the reactants. Those skilled in the art are capable of selecting a suitable organic solvent, and the present invention does not make specific restrictions thereon. Exemplarily, the organic solvent is selected from one or more of dichloroethane, dichloromethane, acetonitrile, methanol, acetone, hexafluoroisopropanol, N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran.

[0028] Furthermore, the light source is selected from one or more of sunlight, fluorescent lamp, mercury lamp, and LEDs; the visible light wavelength provided by the light source is 200 - 800 nm; preferably 380 - 780 nm.

[0029] Furthermore, the reaction temperature of the coupling reaction can be any temperature. Exemplarily, it can be 0 - 60 °C, preferably 10 - 35 °C; the time for the light source to irradiate solution A is 2 - 36 h, and it can be 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h, 30 h, 31 h, 32 h, 33 h, 34 h, 35 h, 36 h, etc.

[0030] Furthermore, the molar ratio of the photocatalyst, the thiol compound, and the nucleophile is 0.05 - 0.2:1 - 3:1, and those skilled in the art can adjust the molar ratio relationship among the three according to the specific required structure. For example, it can be 0.05 - 0.1:1:1, 0.05 - 0.1:2:1, 0.05 - 0.1:3:1, 0.05 - 0.2:1:1, 0.05 - 0.2:2:1, 0.05 - 0.2:3:1, etc.

[0031] In the technical solution of the present invention, an oxygen gas is required as an oxidant to participate in the coupling reaction. The source of oxygen can be directly using the oxygen in the air atmosphere. Therefore, the reaction system only needs to be connected to the atmosphere, or it can also be continuously introducing an oxygen-containing gas to participate in the reaction process. The present invention does not specifically limit the way of introducing oxygen.

[0032] Advantages of the present invention:

[0033] The present invention realizes the direct desulfurization of thiol compounds under photocatalytic conditions to generate carbocations and carry out coupling reactions with various nucleophiles, providing a general and efficient method for converting C-S bonds into C-C bonds or other C-heteroatom bonds, and it is also found that this method has potential application value in the modification of drug molecules.

[0034] The method provided by the present invention has mild conditions and can be realized by irradiating with visible light or sunlight under room temperature and air conditions, without the need for harsh reaction conditions such as high temperature, special ligands, and sacrificial reagents. The whole process is simple, efficient, green, and economical. Description of the drawings

[0035] The following further elaborates on the specific embodiments of the present invention with reference to the drawings.

[0036] Figure 1 1-phenethyl 2-acetoxybenzoate prepared in Example 36 1 1H NMR spectrum;

[0037] Figure 2 1-phenethyl 2-acetoxybenzoate prepared in Example 36 13 13C NMR spectrum;

[0038] Figure 3 1-phenethyl 2-propylpentanoate prepared in Example 37 1 1H NMR spectrum;

[0039] Figure 4 1-phenethyl 2-propylpentanoate prepared in Example 37 13 13C NMR spectrum;

[0040] Figure 5 1-phenethyl 4-(N,N-dipropylaminosulfonyl)benzoate prepared in Example 38 1 1H NMR spectrum;

[0041] Figure 6 1-phenethyl 4-(N,N-dipropylaminosulfonyl)benzoate prepared in Example 38 13 13C NMR spectrum;

[0042] Figure 71H NMR spectrum of N-(1-phenethyl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide prepared in Example 39 1 1H NMR spectrum;

[0043] Figure 8 13C NMR spectrum of N-(1-phenethyl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide prepared in Example 39 13 13C NMR spectrum;

[0044] Figure 9 19F NMR spectrum of N-(1-phenethyl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide prepared in Example 39 19 19F NMR spectrum. Detailed implementation manners

[0045] To illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and drawings. It should be clear that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0046] In addition, unless otherwise specified, the raw materials used in the present invention can be obtained through commercial purchase. Any range described in the present invention includes the end values and any numerical values between the end values, as well as any sub-ranges formed by any numerical values between the end values or the end values.

[0047] In the embodiments of the present invention, the reaction equation for the direct desulfurization of thiol compounds by photocatalysis to generate carbocations and their coupling reactions with various nucleophiles is as follows:

[0048]

[0049] Example 1

[0050] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-phenylethanethiol and add them to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, irradiate solution A with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction is completed, separate by chromatography column. Identify the product as 4-methyl-N-(1-phenethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield is 85%. The NMR spectra and mass spectrometry results are as follows:

[0051] 1 1H NMR (600 MHz, CDCl3) δ 7.69–7.55 (m, 2H), 7.16 (m, 5H), 7.12–7.04 (m, 2H), 5.27 (d, J = 7.2 Hz, 1H), 4.45 (m, 1H), 2.37 (s, 3H), 1.40 (d, J = 6.9 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 143.1, 142.1, 137.6, 129.4, 128.5, 127.4, 127.1, 126.1, 53.6, 23.6, 21.5. ESI-HRMS: m / z calcd for C 15 H 18 NO2S + [M + H] + : 276.1053, found 276.1053.

[0052] Example 2

[0053] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of 4-fluorobenzenesulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as 4-fluoro-N-(1-phenylethyl)benzenesulfonamide by 1H NMR, 13C NMR, 19F NMR and mass spectrometry, and the yield was 87%. The NMR spectra and mass spectrometry results are as follows:

[0054] 1 1H NMR (400 MHz, CDCl3) δ 7.75–7.60 (m, 2H), 7.19–7.10 (m, 3H), 7.06 (m, 2H), 7.02–6.90 (m, 2H), 5.59 (m, 1H), 4.49 (m, 1H), 1.42 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 166.0, 163.5, 141.7, 136.8 (d, J = 3.7 Hz), 129.8 (d, J = 9.5 Hz), 128.6, 127.5, 126.2, 115.9 (d, J = 22.7 Hz), 53.9, 23.7. 1919F NMR (565 MHz, CDCl3) δ -105.81, -105.83, -105.85. 19F NMR (565 MHz, CDCl3) δ -105.32–-106.35 (m). ESI-HRMS: m / z calcd for C 14 H 14 FNNaO2S + [M + Na] + : 302.0622, found 302.0618.

[0055] Example 3

[0056] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of 4-cyanobenzenesulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as 4-cyano-N-(1-phenylethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 60%. The NMR spectra and mass spectrometry results are as follows:

[0057] 1 1H NMR (600 MHz, CDCl3) δ 7.77–7.66 (m, 2H), 7.57 (d, J = 8.2 Hz, 2H), 7.21–7.08 (m, 3H), 7.03 (dd, J = 7.7, 1.8 Hz, 2H), 5.59 (d, J = 7.4 Hz, 1H), 4.56 (t, J = 7.0 Hz, 1H), 1.45 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 145.0, 141.1, 132.5, 128.6, 127.8, 127.6, 126.2, 117.4, 115.7, 54.2, 23.6. ESI-HRMS: m / z calcd for C 15 H 14 N2O2SNa + [M + Na] + 309.0669, found 309.0668.

[0058] Example 4

[0059] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 -A photocatalyst, 0.2 mmol of cyclopropanesulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction was completed, separation was performed by column chromatography. The product was identified as N-(1-phenylethyl)cyclopropanesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 93%. The NMR spectra and mass spectrometry results are as follows:

[0060] 1 1H NMR (400 MHz, CDCl3) δ 7.40–7.32 (m, 4H), 7.31–7.24 (m, 1H), 5.14 (d, J = 7.6 Hz, 1H), 4.63 (m, 1H), 2.03 (m, 1H), 1.54 (d, J = 6.9 Hz, 3H), 1.08–0.93 (m, 2H), 0.75 (m, 1H), 0.70–0.59 (m, 1H). 13 13C NMR (101 MHz, CDCl3) δ 143.4, 128.8, 127.7, 126.2, 53.8, 31.4, 24.4, 6.1, 5.4. ESI-HRMS: m / z calcd for C 11 H 15 NNaO2S + [M+Na] + : 248.0716, found 248.0716.

[0061] Example 5

[0062] 0.01 mmol of Mes-Acr-Ph + BF4 - A photocatalyst, 0.2 mmol of thiophene-2-sulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction was completed, separation was performed by column chromatography. The product was identified as N-(1-phenylethyl)thiophene-2-sulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 69%. The NMR spectra and mass spectrometry results are as follows:

[0063] 1 1H NMR (400 MHz, CDCl3) δ 7.46 (dd, J = 21.3, 4.4 Hz, 2H), 7.26–7.12 (m, 5H), 6.94 (t, J = 4.3 Hz, 1H), 5.41 (d, J = 7.4 Hz, 1H), 4.57 (t, J = 7.0 Hz, 1H), 1.48 (d, J = 6.9 Hz, 3H). 13CNMR(101MHz,CDCl3)δ141.9,141.7,132.3,131.7,128.6,127.6,127.2,126.1,54.1,23.6.ESI-HRMS:m / z calcd for C 12 H 13 NNaO2S2 + [M+Na] + :290.0280,found 290.0274.

[0064] Example 6

[0065] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of naphthalene-1-sulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by column chromatography. The product was identified as N-(1-phenylethyl)naphthalene-1-sulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 29%. The NMR spectra and mass spectrometry results are as follows:

[0066] 1 H NMR(400MHz,CDCl3)δ8.62(d,J=8.5Hz,1H),8.09(dd,J=7.4,1.3Hz,1H),7.92(d,J=8.2Hz,1H),7.85(dd,J=8.1,1.5Hz,1H),7.57(m,2H),7.35(t,J=7.8Hz,1H),7.07–6.78(m,5H),5.38(d,J=7.1Hz,1H),4.46(m,1H),1.33(d,J=6.9Hz,3H). 13 C NMR(151MHz,CDCl3)δ141.4,135.2,134.1,134.1,129.7,129.0,128.2,128.1,127.3,126.7,125.9,124.4,124.0,54.0,23.5.ESI-HRMS:m / z calcd for C 18 H 18 NO2S + [M+H] + :312.1053,found312.1052.

[0067] Example 7

[0068] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of N-methylbenzenesulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by a chromatographic column. The product was identified as N-methyl-N-(1-phenylethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 72%. The NMR spectra and mass spectrometry results are as follows:

[0069] 1 1H NMR (400 MHz, CDCl3) δ 7.89–7.82 (m, 2H), 7.62–7.56 (m, 1H), 7.56–7.49 (m, 2H), 7.31–7.24 (m, 5H), 5.30 (m, 1H), 2.59 (s, 3H), 1.30 (d, J = 7.1 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 140.2, 139.8, 132.4, 129.1, 128.4, 127.6, 127.3, 127.1, 54.9, 28.5, 15.3. ESI-HRMS: m / z calcd for C 15 H 17 NNaO2S + [M + Na] + : 298.0873, found 298.0874.

[0070] Example 8

[0071] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of 4-hydroxybenzenesulfonamide, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by a chromatographic column. The products were identified as 4-hydroxy-N-(1-phenylethyl)benzenesulfonamide and 4-(1-phenylethoxy)-N-(1-phenylethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yields were 60% and 34% respectively.

[0072] The 1H NMR spectra and mass spectrometry results of 4-hydroxy-N-(1-phenylethyl)benzenesulfonamide are as follows:

[0073] 11H NMR (400 MHz, CDCl3) δ 7.67–7.52 (m, 2H), 7.20 (dt, J = 4.6, 1.7 Hz, 3H), 7.14–7.03 (m, 2H), 6.83–6.68 (m, 2H), 5.93 (s, 1H), 4.79 (m, 1H), 4.45 (m, 1H), 1.43 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 159.4, 141.9, 132.1, 129.5, 128.6, 127.6, 126.1, 115.6, 53.7, 23.6. ESI-HRMS: m / z calcd for C 14 H 15 NNaO3S + [M+Na] + : 300.0665, found 300.0658.

[0074] 1H NMR and mass spectrometry results of 4-(1-phenylethoxy)-N-(1-phenylethyl)benzenesulfonamide are as follows:

[0075] 1 1H NMR (400 MHz, CDCl3) δ 7.59–7.46 (m, 2H), 7.43–7.26 (m, 5H), 7.17–6.92 (m, 5H), 6.77 (m, 2H), 5.32 (m, 1H), 4.69 (d, J = 6.8 Hz, 1H), 4.41 (t, J = 6.8 Hz, 1H), 1.65 (d, J = 6.4 Hz, 3H), 1.39 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 161.0, 142.2, 142.1, 142.0, 141.9, 132.1, 132.0, 129.1, 129.0, 128.8, 128.5, 127.9, 127.5, 127.4, 126.1, 126.1, 125.5, 115.7, 53.6, 24.4, 23.6. ESI-HRMS: m / z calcd for C 22 H 23 NNaO3S + [M+Na] + : 404.1291, found 404.1292.

[0076] Example 9

[0077] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 -A photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-(2-methylphenyl)ethane-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction was completed, separation was performed by column chromatography. The product was identified as 4-methyl-N-(1-(o-tolyl)ethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 82%. The NMR spectra and mass spectrometry results are as follows:

[0078] 1 1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 7.9 Hz, 2H), 7.15 (t, J = 7.7 Hz, 3H), 7.09–6.89 (m, 3H), 5.60 (d, J = 7.1 Hz, 1H), 4.75 (m, 1H), 2.37 (s, 3H), 2.22 (s, 3H), 1.38 (d, J = 6.8 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 142.0, 139.3, 136.6, 133.3, 129.3, 128.3, 126.0, 125.9, 125.4, 124.4, 48.7, 22.1, 20.4, 18.0. ESI-HRMS: m / z calcd for C 16 H 19 NO2SNa + [M + Na] + : 312.1029, found 312.1029.

[0079] Example 10

[0080] 0.01 mmol of Mes-Acr-Ph + BF4 - A photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-(3-methylphenyl)ethane-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction was completed, separation was performed by column chromatography. The product was identified as 4-methyl-N-(1-(m-tolyl)ethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 80%. The NMR spectra and mass spectrometry results are as follows:

[0081] 11H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 8.2 Hz, 2H), 7.06 (m, 4H), 6.95 (d, J = 8.5 Hz, 2H), 5.37 (d, J = 7.1 Hz, 1H), 4.35 (m, 1H), 2.31 (s, 3H), 1.29 (d, J = 6.9 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 143.0, 142.0, 138.0, 137.8, 129.3, 128.4, 128.0, 127.1, 126.9, 123.2, 53.7, 23.6, 21.5, 21.3. ESI-HRMS: m / z calcd for C 16 H 19 NO2SNa + [M+Na] + : 312.1029, found 312.1026.

[0082] Example 11

[0083] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-(4-methylphenyl)ethane-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, column chromatography separation was carried out. The product was identified as 4-methyl-N-(1-(p-tolyl)ethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 89%. The NMR spectra and mass spectrometry results are as follows:

[0084] 1 1H NMR (600 MHz, CDCl3) δ 7.70–7.57 (m, 2H), 7.16 (d, J = 8.0 Hz, 2H), 6.98 (s, 4H), 5.26 (d, J = 7.1 Hz, 1H), 4.40 (m, 1H), 2.37 (s, 3H), 2.26 (s, 3H), 1.38 (d, J = 6.9 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 143.0, 139.2, 137.7, 137.0, 129.4, 129.1, 127.1, 126.1, 53.4, 23.5, 21.5, 21.0. ESI-HRMS: m / z calcd for C 16 H 19 NNaO2S + [M+Na]+ : 312.1029, found 312.1035.

[0085] Example 12

[0086] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-([1,1'-biphenyl]-4-yl)ethane-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with blue LED light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as N-(1-([1,1'-biphenyl]-4-yl)ethyl)-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 77%. The NMR spectra and mass spectrometry results are as follows:

[0087] 1 1H NMR (600 MHz, CDCl3) δ 7.62 (d, J = 8.1 Hz, 2H), 7.53–7.47 (m, 2H), 7.44–7.37 (m, 4H), 7.34 (d, J = 7.4 Hz, 1H), 7.15 (m, 4H), 5.22 (d, J = 7.1 Hz, 1H), 4.52 (m, 1H), 2.33 (s, 3H), 1.45 (d, J = 6.9 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 143.1, 141.0, 140.6, 140.4, 137.7, 129.4, 128.8, 127.3, 127.2, 127.1, 127.0, 126.6, 53.4, 23.5, 21.5. ESI-HRMS: m / z calcd for C 21 H 21 NNaO2S + [M+Na] + : 374.1186, found 374.1190.

[0088] Example 13

[0089] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 -The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-(4-fluorophenyl)ethane-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by column chromatography. The product was identified as N-(1-(4-fluorophenyl)ethyl)-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, 19F NMR, and mass spectrometry, with a yield of 79%. The NMR spectra and mass spectrometry results are as follows:

[0090] 1 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 7.8 Hz, 2H), 7.24–6.98 (m, 4H), 6.85 (t, J = 8.5 Hz, 2H), 5.51 (d, J = 7.2 Hz, 1H), 4.45 (m, 1H), 2.39 (s, 3H), 1.38 (d, J = 6.8 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 163.2, 160.8, 143.3, 137.9 (d, J = 3.3 Hz), 137.6, 129.5, 127.9 (d, J = 8.1 Hz), 127.1, 115.3 (d, J = 21.5 Hz). 19 19F NMR (377 MHz, CDCl3) δ -115.11 (ddd, J = 13.8, 8.8, 5.2 Hz). ESI-HRMS: m / z calcd for C 15 H 16 FNNaO2S + [M+Na] + : 316.0778, found 316.0775.

[0091] Example 14

[0092] 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1,2,3,4-tetrahydronaphthalene-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by column chromatography. The product was identified as 4-methyl-N-(1,2,3,4-tetrahydronaphthalen-1-yl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 40%. The NMR spectra and mass spectrometry results are as follows:

[0093] 11H NMR (600 MHz, CDCl3) δ 7.85–7.77 (m, 2H), 7.33 (d, J = 8.0 Hz, 2H), 7.12 (m, 1H), 7.08–7.00 (m, 2H), 6.95 (d, J = 7.7 Hz, 1H), 4.75 (d, J = 7.8 Hz, 1H), 4.49–4.40 (m, 1H), 2.74 (m, 1H), 2.70–2.60 (m, 1H), 2.45 (s, 3H), 1.81 (m, 3H), 1.71 (m, 1H). 13 13C NMR (151 MHz, CDCl3) δ 143.4, 138.2, 137.5, 135.6, 129.8, 129.2, 128.8, 127.6, 127.1, 126.3, 51.9, 30.7, 28.9, 21.6, 19.2. ESI-HRMS: m / z calcd for C 17 H 19 NNaO2S + [M + Na] + : 324.1029, found 324.1028.

[0094] Example 15

[0095] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-(benzo[d][1,3]dioxol-5-yl)ethane-1-thiol and add them to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, irradiate Solution A with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction is completed, separate by column chromatography. Identify the product as N-(1-(benzo[d][1,3]dioxol-5-yl)ethyl)-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield is 50%. The NMR spectra and mass spectrometry results are as follows:

[0096] 1 1H NMR (600 MHz, CDCl3) δ 7.69–7.54 (m, 2H), 7.18 (d, J = 7.9 Hz, 2H), 6.66–6.52 (m, 3H), 5.91–5.78 (m, 2H), 5.51–5.28 (m, 1H), 4.36 (m, 1H), 2.38 (s, 3H), 1.36 (d, J = 6.9 Hz, 3H). 1313C NMR(151MHz,CDCl3)δ147.6,146.8,143.0,137.7,136.2,129.4,127.1,119.7,108.0,106.7,101.0,53.5,23.5,21.5.ESI-HRMS:m / z calcd for C 16 H 17 NNaO4S + [M+Na] + :342.0771,found 342.0775.

[0097] Example 16

[0098] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-(naphthalen-2-yl)ethane-1-thiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by chromatography column. The product was identified as 4-methyl-N-(1-(naphthalen-1-yl)ethyl)benzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 74%. The NMR spectra and mass spectrometry results are as follows:

[0099] 1 1H NMR(600MHz,CDCl3)δ7.95–7.87(m,1H),7.80–7.72(m,1H),7.63(d,J=8.2Hz,1H),7.57–7.49(m,2H),7.45–7.39(m,2H),7.37(dd,J=7.2,1.2Hz,1H),7.25(dd,J=8.2,7.2Hz,1H),6.98(d,J=8.0Hz,2H),5.67(dd,J=9.7,7.0Hz,1H),5.28(m,1H),2.27(s,3H),1.54(d,J=6.8Hz,3H). 13 13C NMR(101MHz,CDCl3)δ143.0,137.9,137.5,133.8,130.2,129.3,128.8,128.0,127.1,126.3,125.6,125.4,123.6,122.7,49.8,23.3,21.4.ESI-HRMS:m / zcalcd for C 19 H 19 NNaO2S + [M+Na] +: 348.1029, found 348.1031.

[0100] Example 17

[0101] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of diphenylmethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by a chromatographic column. The product was identified as N-dibenzyl-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 84%. The NMR spectra and mass spectrometry results are as follows:

[0102] 1 1H NMR (600 MHz, CDCl3) δ 7.60–7.49 (m, 2H), 7.22–7.14 (m, 6H), 7.10 (m, 6H), 5.56 (d, J = 7.4 Hz, 1H), 5.43 (d, J = 7.4 Hz, 1H), 2.35 (s, 3H). 13 13C NMR (151 MHz, CDCl3) δ 143.1, 140.5, 137.4, 129.3, 128.5, 127.5, 127.4, 127.2, 61.3, 21.5. ESI-HRMS: m / z calcd for C 20 H 19 NNaO2S + [M + Na] + : 360.1029, found 360.1028.

[0103] Example 18

[0104] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by a chromatographic column. The product was identified as N-(adamantan-1-yl)-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 90%. The NMR spectra and mass spectrometry results are as follows:

[0105] 11H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.1 Hz, 2H), 7.27 (d, J = 8.1 Hz, 2H), 5.09 (s, 1H), 2.42 (s, 3H), 2.04–1.91 (m, 3H), 1.78 (d, J = 3.1 Hz, 6H), 1.64–1.48 (m, 6H). 13 13C NMR (101 MHz, CDCl3) δ 142.7, 141.3, 129.4, 126.9, 55.0, 43.0, 35.9, 29.5, 21.5. ESI-HRMS: m / z calcd for C 17 H 24 NO2S + [M + H] + : 306.1523 found 306.1519.

[0106] Example 19

[0107] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of 3,5-difluorobenzenesulfonamide, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by column chromatography. The product was identified as N-(adamantan-1-yl)-3,5-difluorobenzenesulfonamide by 1H NMR, 13C NMR, 19F NMR, and mass spectrometry, and the yield was 82%. The NMR spectra and mass spectrometry results are as follows:

[0108] 1 1H NMR (600 MHz, CDCl3) δ 7.46 (m, 2H), 6.99 (m, 1H), 5.27 (s, 1H), 2.03 (m, 3H), 1.81 (d, J = 3.0 Hz, 6H), 1.59 (m, 6H). 13 13C NMR (101 MHz, CDCl3) δ 163.9 (d, J = 11.7 Hz), 161.4 (d, J = 11.7 Hz), 147.5 (t, J = 8.1 Hz), 112.9–109.6 (m), 107.7 (t, J = 25.1 Hz), 55.8, 43.0, 35.8, 29.5. 19 19F NMR (565 MHz, CDCl3) δ -108.22 (dd, J = 9.8, 6.1 Hz). ESI-HRMS: m / z calcd for C 16 H 19 F2NNaO2S +[M+Na] + 350.0997, found 350.0996.

[0109] Example 20

[0110] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of benzenesulfonamide, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by a chromatographic column. The product was identified as N-(adamantan-1-yl)-1-phenylmethanesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 54%. The NMR spectra and mass spectrometry results are as follows:

[0111] 1 1H NMR (600 MHz, CDCl3) δ 7.45–7.31 (m, 5H), 4.22 (s, 2H), 4.11 (s, 1H), 2.14–2.05 (m, 3H), 1.94 (d, J = 2.9 Hz, 6H), 1.66 (d, J = 3.4 Hz, 6H). 13 13C NMR (151 MHz, CDCl3) δ 130.8, 130.0, 128.6, 128.5, 62.4, 55.3, 43.2, 35.9, 29.6. ESI-HRMS: m / z calcd for C 17 H 24 NO2S + [M+H] + 306.1523, found 306.1521.

[0112] Example 21

[0113] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of tert-butyl mercaptan were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by a chromatographic column. The product was identified as N-tert-butyl-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 23%. The NMR spectra and mass spectrometry results are as follows:

[0114] 11H NMR (600 MHz, CDCl3) δ 7.78 (d, J = 7.9 Hz, 2H), 7.31–7.20 (m, 2H), 4.72 (s, 1H), 2.42 (s, 3H), 1.22 (s, 9H). 13 13C NMR (101 MHz, CDCl3) δ 142.8, 140.5, 129.5, 127.0, 54.6, 30.2, 21.5. ESI-HRMS: m / z calcd for C 11 H 18 NO2S + [M + H] + : 228.1053, found 228.1053.

[0115] Example 22

[0116] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 4-methoxybenzyl mercaptan were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, column chromatography was performed. The product was identified as N-(4-methoxybenzyl)-4-methylbenzenesulfonamide by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 30%. The NMR spectra and mass spectrometry results are as follows:

[0117] 1 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.14–7.05 (m, 2H), 6.82–6.73 (m, 2H), 4.92 (t, J = 6.1 Hz, 1H), 4.02 (d, J = 6.1 Hz, 2H), 3.75 (s, 3H), 2.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 159.3, 143.4, 136.9, 129.7, 129.3, 128.4, 127.2, 114.0, 55.3, 46.8, 21.6. ESI-HRMS: m / z calcd for C 15 H 17 NNaO3S + [M + Na] + : 314.0822, found 314.0818.

[0118] Example 23

[0119] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of 4-tert-butylbenzyl mercaptan were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as N-(4-tert-butylbenzyl)-4-methylbenzenesulfonamide by 1H NMR, 13C NMR and mass spectrometry, and the yield was 25%. The NMR spectra and mass spectrometry results are as follows:

[0120] 1 1H NMR (400 MHz, CDCl3) δ 7.86–7.65 (m, 2H), 7.29 (m, 4H), 7.12 (d, J = 8.3 Hz, 2H), 4.61 (s, 1H), 4.11 (d, J = 6.1 Hz, 2H), 2.44 (s, 3H), 1.29 (s, 9H). 13 13C NMR (151 MHz, CDCl3) δ 151.0, 143.4, 136.9, 133.2, 129.7, 127.7, 127.2, 125.6, 47.0, 34.5, 31.3, 21.6. ESI-HRMS: m / z calcd for C 18 H 23 NNaO2S + [M+Na] + : 340.1342, found 340.1344.

[0121] Example 24

[0122] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-toluenesulfonamide, and 0.6 mmol of naphthalene-1-methanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as 4-methyl-N-(naphthalen-1-ylmethyl)benzenesulfonamide by 1H NMR, 13C NMR and mass spectrometry, and the yield was 27%. The NMR spectra and mass spectrometry results are as follows:

[0123] 1 1H NMR (400 MHz, CDCl3) δ 7.90–7.75 (m, 5H), 7.52–7.46 (m, 2H), 7.38–7.27 (m, 4H), 4.55 (m, 3H), 2.45 (s, 3H). 1313C NMR(101MHz,CDCl3)δ143.6,136.6,133.8,131.3,131.2,129.8,129.1,128.8,127.3,126.9,126.7,126.1,125.2,123.2,45.5,21.6.ESI-HRMS:m / z calcd for C 18 H 17 NNaO2S + [M+Na] + :334.0873,found 334.0873.

[0124] Example 25

[0125] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of benzoic acid, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by chromatography column. The product was identified as 1-phenylethyl benzoate by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 63%. The NMR spectra and mass spectrometry results are as follows:

[0126] 1 1H NMR(400MHz,CDCl3)δ8.12–8.05(m,2H),7.58–7.50(m,1H),7.48–7.39(m,4H),7.38–7.33(m,2H),7.32–7.27(m,1H),6.14(m,1H),1.67(d,J=6.6Hz,3H). 13 13C NMR(151MHz,CDCl3)δ165.8,141.8,132.9,130.5,129.6,128.6,128.3,127.9,126.0,72.9,22.4.ESI-HRMS:m / z calcd for C 15 H 14 O2Na + [M+Na] + :249.0886,found 249.0887.

[0127] Example 26

[0128] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 -The photocatalyst, 0.2 mmol of p-toluic acid, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by chromatography column. The product was identified as 1-phenylethyl 4-methylbenzoate by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 88%. The NMR spectra and mass spectrometry results are as follows:

[0129] 1 1H NMR (600 MHz, CDCl3) δ 7.89 (d, J = 7.8 Hz, 2H), 7.36 (d, J = 7.6 Hz, 2H), 7.28 (t, J = 7.5 Hz, 2H), 7.21 (t, J = 7.4 Hz, 1H), 7.15 (d, J = 7.9 Hz, 2H), 6.04 (q, J = 6.6 Hz, 1H), 2.32 (s, 3H), 1.58 (d, J = 6.6 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 165.9, 143.6, 142.0, 129.7, 129.1, 128.6, 127.9, 127.8, 126.1, 72.7, 22.5, 21.7. ESI-HRMS: m / z calcd for C 16 H 16 O2Na + [M+Na] + 263.1043, found 263.1042.

[0130] Example 27

[0131] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of p-tert-butylbenzoic acid, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by chromatography column. The product was identified as 1-phenylethyl 4-tert-butylbenzoate by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 56%. The NMR spectra and mass spectrometry results are as follows:

[0132] 11H NMR (600 MHz, CDCl3) δ 8.02 (d, J = 1.8 Hz, 2H), 7.44 (t, J = 8.2 Hz, 4H), 7.35 (t, J = 7.6 Hz, 2H), 7.28 (t, J = 6.8 Hz, 1H), 6.12 (t, J = 6.6 Hz, 1H), 1.65 (s, 3H), 1.33 (s, 9H). 13 13C NMR (151 MHz, CDCl3) δ 164.0, 154.8, 140.1, 127.7, 126.7, 126.0, 125.9, 124.2, 123.5, 70.8, 33.2, 29.3, 20.6. ESI-HRMS: m / z calcd for C 19 H 22 O2Na + [M + Na] + 305.1512, found 305.1511.

[0133] Example 28

[0134] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of p-fluorobenzoic acid, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by column chromatography. The product was identified as 1-phenylethyl 4-fluorobenzoate by 1H NMR, 13C NMR, 19F NMR, and mass spectrometry, and the yield was 70%. The NMR spectra and mass spectrometry results are as follows:

[0135] 1 1H NMR (600 MHz, CDCl3) δ 8.09 (dd, J = 8.4, 5.5 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.30 (t, J = 7.3 Hz, 1H), 7.10 (t, J = 8.4 Hz, 2H), 6.12 (q, J = 6.6 Hz, 1H), 1.67 (d, J = 6.6 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 167.3, 164.9 (d, J = 29.4 Hz), 141.9, 132.4 (d, J = 9.3 Hz), 128.8, 128.2, 127.1 (d, J = 3.2 Hz), 126.3, 115.6 (d, J = 22.1 Hz), 73.3, 22.5. 1919F NMR (565 MHz, CDCl3) δ -105.75 (q, J = 7.5, 7.0 Hz). ESI-HRMS: m / z calcd for C 15 H 13 FO2Na + [M+Na] + 267.0792, found 267.0791.

[0136] Example 29

[0137] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of benzoic acid, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as adamantan-1-yl benzoate by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 67%. The NMR spectra and mass spectrometry results are as follows:

[0138] 1 1H NMR (400 MHz, CDCl3) δ 8.03–7.92 (m, 2H), 7.57–7.47 (m, 1H), 7.41 (dd, J = 8.4, 6.9 Hz, 2H), 2.29–2.20 (m, 9H), 1.75–1.66 (m, 6H). 13 13C NMR (151 MHz, CDCl3) δ 164.4, 131.3, 131.1, 128.4, 127.1, 80.0, 40.4, 35.2, 29.9. EI-HRMS: m / z calcd for C 17 H 20 O2 + [M] + 256.1463, found 256.1461.

[0139] Example 30

[0140] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 -A photocatalyst, 0.2 mmol of phenylacetic acid, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction was completed, separation was performed by chromatography column. The product was identified as (adamantan-1-yl) 2-phenylacetate by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 52%. The NMR spectra and mass spectrometry results are as follows:

[0141] 1 1H NMR (600 MHz, CDCl3) δ 7.31–7.09 (m, 5H), 3.45 (s, 2H), 2.07 (dd, J = 6.3, 3.5 Hz, 3H), 2.02 (d, J = 3.0 Hz, 6H), 1.57 (d, J = 3.2 Hz, 6H). 13 13C NMR (151 MHz, CDCl3) δ 169.7, 133.8, 128.2, 127.4, 125.8, 79.9, 41.8, 40.2, 35.1, 29.8. ESI-HRMS: m / z calcd for C 18 H 22 O2Na + [M+Na] + 293.1512, found 293.1513.

[0142] Example 31

[0143] Weighed 0.01 mmol of Mes-Acr-Ph + BF4 - A photocatalyst, 0.2 mmol of phenethyl alcohol, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction was completed, separation was performed by chromatography column. The product was identified as 1-phenethoxyadamantane by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 35%. The NMR spectra and mass spectrometry results are as follows:

[0144] 1 1H NMR (600 MHz, CDCl3) δ 7.31–7.16 (m, 5H), 3.60 (t, J = 7.6 Hz, 2H), 2.83 (t, J = 7.6 Hz, 2H), 2.12 (t, J = 3.5 Hz, 3H), 1.73 (d, J = 2.9 Hz, 6H), 1.64–1.54 (m, 6H). 1313C NMR (151 MHz, CDCl3) δ 139.4, 129.0, 128.2, 126.0, 72.2, 61.3, 41.6, 37.6, 36.5, 30.5. ESI-HRMS: m / z calcd for C 18 H 24 NaO + [M + Na] + 279.1720, found 279.1720.

[0145] Example 32

[0146] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of water, and 0.6 mmol of 1-adamantanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as adamantan-1-ol by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 19%. The NMR spectra and mass spectrometry results are as follows:

[0147] 1 1H NMR (400 MHz, CDCl3) δ 2.22–2.05 (m, 3H), 1.71 (d, J = 3.1 Hz, 6H), 1.63 (t, J = 10.6 Hz, 6H). 13 13C NMR (151 MHz, CDCl3) δ 67.2, 44.3, 35.1, 29.7. EI-HRMS: m / z calcd for C 10 H 16 O + [M] + 152.1201, found 152.1196.

[0148] Example 33

[0149] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of anisole, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as 1-methoxy-4-(1-phenylethyl)benzene by 1H NMR, 13C NMR, and mass spectrometry, and the yield was 41%. The NMR spectra and mass spectrometry results are as follows:

[0150] 1 1H NMR (600 MHz, CDCl3) δ 7.27 (m, 2H), 7.23–7.07 (m, 5H), 6.82 (d, J = 8.2 Hz, 2H), 4.10 (m, 1H), 3.77 (s, 3H), 1.61 (d, J = 7.2 Hz, 3H). 13 13C NMR (151 MHz, CDCl3) δ 157.8, 146.8, 138.6, 128.5, 128.4, 127.6, 126.0, 113.7, 55.3, 43.9, 22.1. EI-HRMS: m / z calcd for C 15 H 16 O + [M] + 212.1201, found 212.1196.

[0151] Example 34

[0152] Weigh 0.01 mmol of Mes-Acr-Ph+BF4- photocatalyst, 0.2 mmol of p-tert-butylbenzenethiol, and 0.6 mmol of 1-phenylethanethiol and add them to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, irradiate solution A with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction is completed, separate by column chromatography. The product is identified as (1-(4-(tert-butyl)phenyl)ethyl)(1-phenylethyl)sulfane by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 18%. The NMR spectra and mass spectrometry results are as follows:

[0153] 1 1H NMR (600 MHz, CDCl3) δ 7.26 (m, 9H), 4.29 (q, J = 7.0 Hz, 1H), 1.62 (d, J = 7.0 Hz, 3H), 1.28 (s, 9H). 13 13C NMR (151 MHz, CDCl3) δ 150.45, 143.40, 132.47, 131.60, 128.38, 127.30, 127.07, 125.74, 48.17, 34.52, 31.26, 22.40. EI-HRMS: m / z calcd for C 18 H 22 S + [M] + 270.1442, found 270.1440.

[0154] Example 35

[0155] Weigh 0.01 mmol of Mes-Acr-Ph+BF4- photocatalyst, 0.2 mmol of N-(p-toluenesulfonyl)indole, and 0.6 mmol of 1-phenylethanethiol, and add them to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, irradiate solution A with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction is completed, separate by column chromatography. Identify the product as 3-(1-phenylethyl)-1-toluenesulfonyl-1H-indole by 1H NMR, 13C NMR, and mass spectrometry, with a yield of 18%. The NMR spectra and mass spectrometry results are as follows:

[0156] 1 1H NMR (400 MHz, CDCl3) δ 7.94 (dd, J = 8.3, 1.0 Hz, 1H), 7.78–7.70 (m, 2H), 7.42 (d, J = 1.3 Hz, 1H), 7.25–7.14 (m, 8H), 7.07 (m, 1H), 4.26–4.15 (m, 1H), 2.35 (s, 3H), 1.66 (d, J = 7.1 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 144.9, 144.7, 135.7, 135.3, 130.5, 129.8, 128.5, 127.7, 127.3, 126.8, 126.4, 124.6, 123.0, 122.9, 120.3, 113.8, 36.9, 22.0, 21.6. ESI-HRMS: m / z calcd for C 23 H 22 NO2S + [M + H] + : 376.1366, found 376.1365.

[0157] Example 36

[0158] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of 2-acetoxybenzoic acid (aspirin), and 0.6 mmol of 1-phenylethanethiol, and add them to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, irradiate solution A with LED blue light (wavelength 460 - 465 nm) for 8 h to carry out the reaction. After the reaction is completed, separate by column chromatography. Identify the product as phenethyl 2-acetoxybenzoate (see Figure 1 and Figure 2 ), with a yield of 39%. The NMR spectra and mass spectrometry results are as follows:

[0159] 11H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 7.8, 1.7 Hz, 1H), 7.53 (ddd, J = 8.1, 7.4, 1.7 Hz, 1H), 7.45–7.39 (m, 2H), 7.36 (m, 2H), 7.33–7.25 (m, 2H), 7.08 (dd, J = 8.1, 1.2 Hz, 1H), 6.10 (q, J = 6.6 Hz, 1H), 2.20 (s, 3H), 1.65 (d, J = 6.6 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 169.6, 163.9, 150.6, 141.3, 133.7, 131.8, 128.6, 128.0, 126.2, 126.0, 123.8, 73.2, 22.1, 20.9. ESI-HRMS: m / z calcd for C 17 H 16 O4Na + [M + Na] + 307.0941, found 307.0933.

[0160] Example 37

[0161] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - photocatalyst, 0.2 mmol of valproic acid, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain solution A. Under room temperature and air conditions, solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by chromatography column. The product was identified as 1-phenethyl 2-propylvalerate by 1H NMR, 13C NMR and mass spectrometry (see Figure 3 and Figure 4 ), and the yield was 30%. The NMR spectra and mass spectrometry results are as follows:

[0162] 1 1H NMR (600 MHz, CDCl3) δ 7.39–7.30 (m, 4H), 7.29–7.25 (m, 1H), 5.91 (m, 1H), 2.39 (m, 1H), 1.64–1.55 (m, 2H), 1.52 (d, J = 6.6 Hz, 3H), 1.44–1.36 (m, 2H), 1.32–1.25 (m, 2H), 1.22 (m, 2H), 0.89 (t, J = 7.3 Hz, 3H), 0.85 (t, J = 7.3 Hz, 3H). 1313C NMR (151 MHz, CDCl3) δ 175.7, 141.9, 128.4, 127.7, 126.0, 71.7, 45.4, 34.7, 34.6, 22.3, 20.6, 20.5, 14.0. ESI-HRMS: m / z calcd for C16H24NaO2 + [M+Na] + 271.1669, found 271.1667.

[0163] Example 38

[0164] Weigh 0.01 mmol of Mes-Acr-Ph + BF4 - The photocatalyst, 0.2 mmol of probenecid, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction, separation was carried out by column chromatography. The product was identified as 1-phenylethyl 4-(N,N-dipropylaminosulfonyl)benzoate (see Figure 5 and Figure 6 ) with a yield of 35%. The NMR spectra and mass spectrometry results are as follows:

[0165] 1 1H NMR (400 MHz, CDCl3) δ 8.22–8.14 (m, 2H), 7.91–7.83 (m, 2H), 7.49–7.42 (m, 2H), 7.40–7.31 (m, 3H), 6.15 (m, 1H), 3.18–3.03 (m, 4H), 1.70 (d, J = 6.6 Hz, 3H), 1.58–1.49 (m, 4H), 0.87 (t, J = 7.4 Hz, 6H). 13 13C NMR (151 MHz, CDCl3) δ 164.5, 144.2, 141.2, 133.8, 130.3, 128.7, 128.2, 127.0, 126.1, 73.8, 49.9, 22.3, 21.9, 11.2. ESI-HRMS: m / z calcd for C 21 H 28 NO4S + [M+H] + 390.1734, found 390.1740.

[0166] Example 39

[0167] Weigh 0.01 mmol of Mes-Acr-Ph + BF4- The photocatalyst, 0.2 mmol of celecoxib, and 0.6 mmol of 1-phenylethanethiol were added to 2 mL of dichloroethane to obtain Solution A. Under room temperature and air conditions, Solution A was irradiated with LED blue light (wavelength 460 - 465 nm) for 8 h for the reaction. After the reaction was completed, separation was carried out by a chromatographic column. The product was identified as N-(1-phenethyl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide by 1H NMR, 13C NMR, 19F NMR, and mass spectrometry (see Figure 7 , Figure 8 and Figure 9 ), and the yield was 76%. The NMR spectra and mass spectrometry results are as follows:

[0168] 1 H NMR (400 MHz, CDCl3) δ 7.77–7.59 (m, 2H), 7.36–7.28 (m, 2H), 7.25–7.13 (m, 5H), 7.13–7.00 (m, 4H), 6.72 (s, 1H), 5.34 (d, J = 7.1 Hz, 1H), 4.50 (m, 1H), 2.37 (s, 3H), 1.42 (d, J = 6.9 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 145.2, 144.3, 143.9, 142.3, 141.8, 140.4, 139.7, 129.7, 128.7 (d, J = 9.2 Hz), 128.0, 127.7, 126.1, 125.9, 125.2, 122.5, 119.8, 106.3, 53.9, 23.5, 21.5. 19 19F NMR (565 MHz, CDCl3) δ -62.41. ESI-HRMS: m / z calcd for C 25 H 23 F3N3O2S + [M + H] + 486.1458, found 486.1458.

[0169] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly explaining the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to enumerate all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A method for photocatalytically generating carbocations from thiol compounds and carrying out a coupling reaction with a nucleophile, characterized in that, It includes the following steps: Add a photocatalyst, a thiol compound, and a nucleophile into an organic solvent to obtain solution A; In an oxygen-containing environment, irradiate solution A with a light source. Under the action of the photocatalyst, the thiol compound undergoes desulfurization to generate a carbocation, and then the carbocation undergoes a coupling reaction with the nucleophile.

2. The method according to claim 1, characterized in that, The thiol compound is selected from the compounds having the structure shown in Formula I: Among them, R1, R2 and R3 are each independently selected from H, C1-C 20 alkyl, aryl, C1-C 12 alkoxy, COO t Bu, allyl, F, Cl, Br, any one of them.

3. The method according to claim 2, wherein The aryl group is selected from any one of a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group, and the substituent is selected from any one of an alkyl group, an alkoxy group, F, Cl, and Br.

4. The method according to claim 1, wherein The thiol compound is selected from one or more of 1-phenylethanethiol, 1-adamantanethiol, 1-(naphthalen-2-yl)ethane-1-thiol, 1-(4-fluorophenyl)ethane-1-thiol, 1-(2-methylphenyl)ethane-1-thiol, 1-(3-methylphenyl)ethane-1-thiol, 1-(4-methylphenyl)ethane-1-thiol, 1-(4-chloro)phenyl ethanethiol, 1-([1,1'-biphenyl]-4-yl)ethane-1-thiol, 1,2,3,4-tetrahydronaphthalene-1-thiol, 1-(benzo[d][1,3]dioxol-5-yl)ethane-1-thiol, diphenylmethanethiol, tert-butylthiol, 4-methoxybenzylthiol, 4-tert-butylbenzylthiol, 1-naphthalenemethanethiol.

5. The method according to claim 1, wherein The nucleophile is selected from the structures shown in any one of the following Formulas II-1 to II-8: Wherein, In Formula II-1, R4 and R5 are each independently selected from any one of H, an alkyl group, an aryl group, and an alkoxy group; In formula II-2, R6, R7, and R8 are each independently selected from any one of H, OMe, t Bu, i Pr, Et, and Me; In Formula II-3, R9 is selected from any one of H, an alkyl group, an aryl group, and an alkoxy group; In formula II-4, R 10 is selected from any one of H, alkyl, aryl, and alkoxy; In formula II-5, R 11 is selected from H or alkyl; In formula II-6, R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from any one of H, aryl, alkoxy, alkyl, methoxy, allyl, and Cl; In formula II-7, R 19 and R 20 each independently selected from any one of H, CHO, COMe, COOMe, COOEt, and X1 and X2 are each independently selected from N or C; In formula II-8, R 21 is selected from alkyl or aryl.

6. The method according to claim 1, wherein The nucleophile is selected from one or more of p-toluenesulfonamide, 4-fluorobenzenesulfonamide, p-cyanobenzenesulfonamide, cyclopropanesulfonamide, thiophene-2-sulfonamide, naphthalene-1-sulfonamide, N-methylbenzenesulfonamide, 4-hydroxybenzenesulfonamide, p-toluenesulfonamide, 3,5-difluorobenzenesulfonamide, benzenesulfonamide, benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-fluorobenzoic acid, phenylacetic acid, water, anisole, p-tert-butylbenzenethiol, N-(p-toluenesulfonyl)indole, valproic acid, probenecid, celecoxib, aspirin.

7. The method according to claim 1, wherein The photocatalyst is selected from one or more of 9-mesityl-10-phenylacridin-10-ium tetrafluoroborate, 9-mesityl-10-methylacridinium perchlorate, 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile, eosin Y, rhodamine 6G, anthraquinone, fluorescein, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bipyridine(4-tert-butylpyridine)]iridium bis(hexafluorophosphate), tris(2-phenylpyridine)iridium, (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2-pyridyl)phenyl]iridium(III) hexafluorophosphate.

8. The method according to claim 1, characterized in that, The organic solvent is selected from one or more of dichloroethane, dichloromethane, acetonitrile, methanol, acetone, hexafluoroisopropanol, N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran.

9. The method according to claim 1, wherein The light source is selected from one or more of sunlight, fluorescent lamp, mercury lamp, and LEDs; the visible light wavelength provided by the light source is 200 - 800 nm; The reaction temperature of the coupling reaction is 0 - 60 °C, and the time for the light source to irradiate solution A is 2 - 36 h.

10. The method according to claim 1, wherein The molar ratio of the photocatalyst, thiol compound, and nucleophile is 0.05 - 0.2:1 - 3:1.

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