Gamma-carbonyl sulfone derivative and photocatalytic synthesis method thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a gamma-carbonyl sulfone derivative and a photocatalytic synthesis method thereof. The photocatalytic synthesis method of the gamma-carbonyl sulfone derivative comprises the following steps: adding a beta, gamma-unsaturated ketone compound, a sulfonyl chloride compound, a photocatalyst, alkali and an additive into a solvent, carrying out photocatalytic reaction, and then separating and purifying to obtain the gamma-carbonyl sulfone derivative. The reaction has the advantages of cheap and easily available raw materials, low reaction cost and mild reaction conditions; the operation is simple, and a target product can be efficiently obtained. The photocatalytic synthesis method of the gamma-carbonyl sulfone derivative has good universality to the raw materials, the raw materials are wide in source, the target product is easy to separate under optimized reaction conditions, and the photocatalytic synthesis method has potential application value in the fields of materials and medicines.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a gamma-carbonyl sulfone derivative and a photocatalytic synthesis method thereof. Background Art

[0002] Sulfone derivatives are widely found in natural products, functional materials and medicinal chemistry. With the development of photocatalysis, visible light-induced sulfonylation has gradually become an important means of synthesizing sulfone compounds. Among them, the 1,2-hydrosulfonylation of olefins has been a highly concerned area and has made considerable progress. a) SM Hell, CF Meyer, A. Misale, JBI Sap, KE Christensen, MC Willis, AA Trabanco and V.Gouverneur, Angew. Chem. Int. Ed ., 2020,59, 11620-11626. b) JJ Wang and W.Yu, Org. Lett ., 2019,21, 9236-9240. c) Y. Chen, N. McNamara, O. May, T.Pillaiyar, DC Blakemore and SV Ley, Org. Lett . 2020,22, 5746-5748. d) X.Du, JS Zhen, XH Xu, H. Yuan, YH Li, Y. Zheng, C. Xue and Y. Luo, Org. Lett . 2022,24, 3944-3949. e) Y. Song, C. Li, X. Hu, H. Zhang, Y. Mao, X.Wang, C. Wang, L. Hu and J. Yan, Green Chem ., 2024,26, 6578-6583. f) SMHell, CF Meyer, G. Laudadio, A. Misale, MC Willis, T. Noël, AATrabanco and V. Gouverneur, J. Am. Chem. Soc., 2019,142, 720-725. g) DD Vos,AV Cunha, BB Jei and BUW Maes, ACS Catal.,2024,14, 12282-12296. h)P. Das, S. Das, K. Varalaxmi and R. Jana, Adv. Synth. Catal., 2021,363, 575-584. In the existing literature, most of the work focuses on 1,2-hydrogensulfonylation reactions. There are few reports on hydrosulfonylation reactions at the distal end of unsaturated double bonds, especially 1,3-hydrogensulfonylation reactions.

[0003] With the development of free radical-mediated 1,n-difunctionalization reactions, especially the research on 1,3-difunctionalization reactions in recent years, F. Chen, Z. Cao and C. Zhu, Chem. Commun., 2024,60, 14912-14923. j)K. Jana, A. Bhunia and A. Studer, Chem . , 2020,6, 512-522. k) R. Liu, Y. Tian,J. Wang, Z. Wang, X. Li, C. Zhao, R. Yao, S. Li, L. Yuan, J. Yang and D. Shi, Sci. Adv. 2022, 8, eabq8596. It is envisaged to combine the 1,2-carbonyl migration process with the hydrosulfonylation reaction to achieve the 1,3-hydrosulfonylation reaction of β,γ-unsaturated ketones.

[0004] However, the current conventional hydrosulfonylation reaction, which selectively protonates at position 2, suffers from site selectivity limitations. Therefore, there is an urgent need to find a novel sulfonylation reaction with selective protonation at position 3 to expand the methods for synthesizing γ-carbonylsulfone derivatives. Summary of the Invention

[0005] In order to overcome the shortcomings of the above-mentioned existing site-selective technology, the purpose of the present invention is to provide a new photocatalytic synthesis method for synthesizing γ-carbonyl sulfone derivatives by selective protonation sulfonylation reaction at position 3, so as to solve the site selectivity shortcomings of traditional hydrosulfonylation reaction.

[0006] In order to achieve the above object, the present invention proposes a photocatalytic synthesis method of γ-carbonyl sulfone derivatives, and the technical solution adopted is: A photocatalytic synthesis method for γ-carbonyl sulfone derivatives comprises the following steps: adding a β,γ-unsaturated ketone compound, a sulfonyl chloride compound, a photocatalyst, a base, and an additive to a solvent, performing a photocatalytic reaction, and then separating and purifying to obtain a γ-carbonyl sulfone derivative as shown in formula (I);

[0007] Among them, R 1 is selected from hydrogen, alkyl, trifluoromethoxy, halogen, ester, cyano or heterocycle; R 2 is selected from hydrogen, alkyl, phenyl, methoxy, halogen, cyano or fused ring.

[0008] The beneficial effects of the present invention are: The invention discloses a photocatalytic synthesis method of γ-carbonyl sulfone derivatives. The method comprises the following steps: reacting a β,γ-unsaturated ketone compound and a sulfonyl chloride compound in a photocatalytic system to synthesize the γ-carbonyl sulfone derivatives. The reaction can be carried out rapidly at room temperature. The β,γ-unsaturated ketone compound acts as a free radical acceptor and exhibits good selectivity in the photocatalytic reaction. At the same time, due to its inherent properties, the sulfonyl chloride compound is easily reduced by a single electron under photocatalytic conditions to form a sulfonyl radical intermediate and a chloride anion. The sulfonyl chloride can complete free radical addition with the unsaturated bond of the β,γ-unsaturated ketone compound, and further undergoes 1,2-carbonyl migration on the basis of the free radical addition to obtain a tertiary carbon radical after translocation and achieve protonation, thereby completing the synthesis of the γ-carbonyl sulfone derivatives in one step. In the photocatalytic synthesis method of γ-carbonyl sulfone derivatives of the present application, after the β,γ-unsaturated ketone compounds undergo free radical addition with the sulfonyl radical, a rapid intramolecular 1,2-carbonyl migration is carried out in series to achieve efficient selective protonation at the 3rd position, indicating that the idea of ​​synthesizing γ-carbonyl sulfone derivatives through 1,3-hydrogensulfonylation reaction is theoretically feasible.

[0009] The photocatalytic synthesis method for γ-carbonylsulfone derivatives disclosed in this application is carried out at room temperature, under mild reaction conditions, with broad functional group tolerance and high reaction efficiency. This method is of great significance for the one-step synthesis of γ-carbonylsulfone derivatives, with product yields reaching up to 92%. Compared to traditional 1,2-hydrosulfonylation reactions, the photocatalytic synthesis method for γ-carbonylsulfone derivatives disclosed in this application exhibits novel and highly efficient site selectivity, utilizes readily available and inexpensive raw materials, and is environmentally friendly. The reaction is highly adaptable to a wide range of raw materials, and under optimized reaction conditions, the target product is easily isolated, demonstrating potential applications in the materials and pharmaceutical fields.

[0010] In order to make the β,γ-unsaturated ketone compound exhibit better selectivity as a free radical acceptor in the photocatalytic reaction, preferably, the general structural formula of the β,γ-unsaturated ketone compound is as shown in formula (II):

[0011] Among them, R 1 is selected from hydrogen, alkyl, trifluoromethoxy, halogen, ester, cyano or heterocycle.

[0012] In order to further improve the selectivity of β,γ-unsaturated ketone compounds, preferably, the β,γ-unsaturated ketone compound is selected from 2,2-dimethyl-1-phenylbut-3-ene-1-one, 2,2-dimethyl-1-(4-(trifluoromethoxy)phenyl)but-3-ene-1-one, 4-(2,2-dimethylbut-3-enoyl)benzoic acid methyl ester, 3-(2,2-dimethylbut-3-enoyl)benzonitrile, 2,2-dimethyl-1-(o-tolyl)but-3-ene-1-one, 1-(2-bromophenyl)-2,2-dimethylbut-3-ene-1-one, 1-(2-bromo-4-chlorophenyl)-2,2-dimethylbut-3-ene-1-one or 2,2-dimethyl-1-(4-(pyridin-2-yl)phenyl)but-3-ene-1-one.

[0013] In order to allow the sulfonyl chloride compound to be reduced by a single electron under photocatalytic conditions to form a sulfonyl radical intermediate and a chloride anion, preferably, the general structural formula of the sulfonyl chloride compound is as shown in formula (III):

[0014] Among them, R 2 is selected from hydrogen, alkyl, phenyl, methoxy, halogen, cyano or fused ring.

[0015] In order to promote the migration of 1,2-carbonyl groups on the basis of free radical addition, obtain tertiary carbon radicals after metathesis and achieve protonation, preferably, the sulfonyl chloride compound is selected from one of 4-toluenesulfonyl chloride, benzenesulfonyl chloride, 4-iodobenzenesulfonyl chloride, 4-phenoxybenzenesulfonyl chloride, 3-cyanobenzenesulfonyl chloride, 2-methoxybenzenesulfonyl chloride, 2-naphthalenesulfonyl chloride or ethylsulfonyl chloride.

[0016] In order to fully complete the free radical addition of the sulfonyl chloride compound and the β,γ-unsaturated ketone compound, and further promote the 1,2-carbonyl migration on the basis of the free radical addition, preferably, the molar ratio of the β,γ-unsaturated ketone compound to the sulfonyl chloride compound is 1.0: (1.2 – 1.8).

[0017] In order to promote the full photocatalytic reaction between sulfonyl chloride compounds and β,γ-unsaturated ketone compounds, preferably, the photocatalyst is Eosin Y, and the molar ratio of Eosin Y to β,γ-unsaturated ketone compounds is (0.01-0.03):1.0; the base is Na3PO4, and the molar ratio of Na3PO4 to β,γ-unsaturated ketone compounds is (1.5-2.5):1; the additive is 4-methylthiophenol, and the molar ratio of 4-methylthiophenol to β,γ-unsaturated ketone compounds is (1.5-2.5):1; the solvent is hexafluoroisopropanol, isopropanol or dimethyl sulfoxide, and the ratio of the volume of the solvent to the molar amount of the β,γ-unsaturated ketone compound is (0.5-1) mL:0.1 mmol.

[0018] In order to further promote the photocatalytic reaction, fully react the raw materials, and maximize the product yield, preferably, the conditions of the photocatalytic reaction are: stirring for 10 to 15 hours at room temperature under 15 to 30 W blue LED irradiation.

[0019] In order to obtain γ-carbonyl sulfone derivatives, preferably, the separation and purification conditions are as follows: after the photocatalytic reaction, deionized water is first added to quench the reaction, and then extracted with ethyl acetate 2 to 4 times, the ethyl acetate is collected and dried with anhydrous sodium sulfate, filtered, and reduced pressure before flash chromatography to finally obtain γ-carbonyl sulfone derivatives.

[0020] The present invention also provides a γ-carbonyl sulfone derivative, which is synthesized by the above-mentioned photocatalytic synthesis method of the γ-carbonyl sulfone derivative. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the NMR spectrum of the product prepared in Example 1, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 2 This is the NMR spectrum of the product prepared in Example 2, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 3 This is the NMR spectrum of the product prepared in Example 3, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 4 This is the NMR spectrum of the product prepared in Example 4, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 5 This is the NMR spectrum of the product prepared in Example 5, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 6 This is the NMR spectrum of the product prepared in Example 6, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 7 This is the NMR spectrum of the product prepared in Example 7, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 8 This is the NMR spectrum of the product prepared in Example 8, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 9 This is the NMR spectrum of the product prepared in Example 9, where (a) is 1 H NMR spectrum, (b) 13 C NMR spectrum; Figure 10 This is the NMR spectrum of the product prepared in Example 10, wherein (a) is 1 H NMR spectrum, (b) 13 CNMR spectra; Figure 11 This is the NMR spectrum of the product prepared in Example 11, wherein (a) is 1 H NMR spectrum, (b) 13 CNMR spectra; Figure 12 This is the NMR spectrum of the product prepared in Example 12, wherein (a) is 1 H NMR spectrum, (b) 13 CNMR spectra; Figure 13 This is the NMR spectrum of the product prepared in Example 13, wherein (a) is 1 H NMR spectrum, (b) 13 CNMR spectra; Figure 14 This is the NMR spectrum of the product prepared in Example 14, wherein (a) is 1 H NMR spectrum, (b) 13 CNMR spectra; Figure 15This is the NMR spectrum of the product prepared in Example 15, wherein (a) is 1 H NMR spectrum, (b) 13 CNMR spectrum. DETAILED DESCRIPTION

[0022] Conventional hydrosulfonylation reactions in the prior art suffer from site selectivity limitations. The present invention provides a photocatalytic synthesis method for γ-carbonyl sulfone derivatives, comprising the following steps: adding a β,γ-unsaturated ketone compound, a sulfonyl chloride compound, a photocatalyst, a base, and an additive to a solvent; performing a photocatalytic reaction; and then separating and purifying the resulting γ-carbonyl sulfone derivatives to obtain the derivatives shown in formula (I);

[0023] Among them, R 1 is selected from hydrogen, alkyl, trifluoromethoxy, halogen, ester, cyano or heterocycle; R 2 is selected from hydrogen, alkyl, phenyl, methoxy, halogen, cyano or fused ring.

[0024] The technical concept of the present invention is: the β,γ-unsaturated ketone compounds in the present invention act as free radical acceptors and show good selectivity in photocatalytic reactions, mainly providing unsaturated bonds; sulfonyl chloride compounds are easily reduced by single electrons under photocatalytic conditions to form sulfonyl radical intermediates and chloride anions; the sulfonyl radical intermediates and chloride anions of the sulfonyl chloride compounds can complete free radical addition with the unsaturated bonds of the β,γ-unsaturated ketone compounds, and on the basis of the free radical addition, further undergo 1,2-carbonyl migration to obtain tertiary carbon radicals after translocation and achieve protonation, thereby completing the synthesis of γ-carbonyl sulfone derivatives in one step. In the photocatalytic synthesis method of γ-carbonyl sulfone derivatives of the present application, after the β,γ-unsaturated ketone compounds undergo free radical addition with the sulfonyl radical, a rapid intramolecular 1,2-carbonyl migration is carried out in series to achieve efficient selective protonation at position 3. Compared with the traditional 1,2-hydrogensulfonylation reaction, the photocatalytic synthesis method of γ-carbonylsulfone derivatives of the present application exhibits novel and efficient site selectivity, the raw materials are cheap and easily available, the reaction cost is low, and it is environmentally friendly; the reaction has good universality for the raw materials, the sources of the raw materials are wide, and under optimized reaction conditions, the target product is easy to separate, and it has potential application value in the fields of materials and medicine.

[0025] Specifically, the photocatalytic synthesis method of γ-carbonyl sulfone derivatives includes the following steps: adding a β,γ-unsaturated ketone compound represented by formula II and a sulfonyl chloride compound represented by formula III to a hexafluoroisopropanol solvent, then adding Eosin Y, Na3PO4 and 4-toluene thiophenol, replacing the air with argon and sealing; then placing it under 15-30 W blue light LED irradiation at room temperature and stirring for 10-15 hours to carry out a photocatalytic reaction. After the reaction is complete, deionized water is added to quench the reaction, and the organic phase is extracted with ethyl acetate 2-4 times, and the organic phase is collected and dried with anhydrous sodium sulfate to remove moisture. After filtering, the solvent is removed under reduced pressure and flash chromatography is performed to obtain γ-carbonyl sulfone derivatives. Among them, the molar ratio of β,γ-unsaturated ketone compounds to sulfonyl chloride compounds is 1.0: (1.2-1.8); the molar ratio of Eosin Y to β,γ-unsaturated ketone compounds is (0.01-0.03):1; the molar ratio of Na3PO4 to β,γ-unsaturated ketone compounds is (1.5-2.5):1; the molar ratio of 4-methylthiophenol to β,γ-unsaturated ketone compounds is (1.5-2.5):1; and the ratio of the volume of hexafluoroisopropanol to the molar amount of β,γ-unsaturated ketone compounds is (0.5-1) mL:0.1 mmol. Specifically, the reaction formula of β,γ-unsaturated ketone compound and sulfonyl chloride compound is:

[0026] Among them, R 1 is selected from hydrogen, alkyl, trifluoromethoxy, halogen, ester, cyano or heterocycle; R 2 is selected from hydrogen, alkyl, phenyl, methoxy, halogen, cyano or fused ring.

[0027] Specifically, the solvent is hexafluoroisopropanol.

[0028] The implementation process of the present invention is described in detail below in conjunction with specific embodiments. However, it will be understood by those skilled in the art that the following embodiments are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should also be noted that, for ease of description, only the parts relevant to the invention are shown in the embodiments. It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to the embodiments. It should be noted that the endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0029] In the following examples and comparative examples, among the raw materials used, the CAS number of Eosin Y is 17372-87-1, and the remaining raw materials are common commercial products that can be directly purchased or can be prepared according to conventional techniques in the art.

[0030] 1. Example of the Photocatalytic Synthesis Method of γ-Carbonylsulfone Derivatives of the Present Invention Example 1 The γ-carbonyl sulfone derivative provided in Example 1 is 3-Methyl-1-phenyl-2-(tosylmethyl)butan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol) and 4-toluenesulfonyl chloride (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 58.7 mg of white solid, the yield is 89%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0031] like Figure 1 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.0 Hz,2H), 7.67 (d, J = 8.0 Hz, 2H), 7.55 (t, J = 7.1 Hz, 1H), 7.43 (t, J= 7.6 Hz, 2H),7.18 (d, J = 8.0 Hz, 2H), 4.02 (dd, J = 13.1, 10.5 Hz, 1H), 3.95 (dd, J = 10.2, 4.0Hz, 1H), 3.15 (d, J = 13.5 Hz, 1H), 2.34 (s, 3H), 2.09 – 2.00 (m, 1H), 0.97 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 199.3, 144.7,136.5, 136.2, 133.3, 129.8, 128.7, 128.5, 128.2, 54.4, 46.1, 30.8, 21.6,20.8, 18.3.HRMS(ESI) m / z: [M+H] + Calcd. for C 19 H 23 O3S: 331.1362, Found 331.1364. Example 2 The γ-carbonyl sulfone derivative provided in Example 2 is 3-Methyl-2-(tosylmethyl)-1-(4-(trifluoromethoxy)phenyl)butan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-(4-(trifluoromethoxy)phenyl)but-3-en-1-one (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol) and 4-toluenesulfonyl (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 30 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 76.2 mg of white solid, the yield is 92%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The obtained product structure is as follows: .

[0032] like Figure 2 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.9 Hz,2H), 7.67 (d, J = 7.5 Hz, 2H), 7.28 (d, J = 8.8 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H),4.02 – 3.96 (m, 1H), 3.92 (dd, J = 10.4, 4.6 Hz, 1H), 3.16 (d, J = 13.4 Hz, 1H), 2.37 (s, 3H), 2.07 – 1.99 (m, 1H), 0.97 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.7 Hz,3H). 13 C NMR (101 MHz, CDCl3) δ 198.2, 152.9, 144.9, 136.2, 134.9, 130.6, 129.9,128.2, 120.5, 120.4 (q, J = 260 Hz), 54.7, 46.1, 31.0, 21.7, 20.8, 18.5. 19 F NMR(376 MHz, CDCl3) δ -57.60.HRMS(ESI) m / z: [M+H] + Calcd. For C 20 H 22 F3O4S: 415.1185,Found 415.1189. Example 3 The γ-carbonyl sulfone derivative provided in Example 3 is Methyl 4-(3-methyl-2-(tosylmethyl)butanoyl)benzoate, and the photocatalytic synthesis method thereof comprises the following steps: Methyl 4-(2,2-dimethylbut-3-enoyl)benzoate (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 15 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 2: 1), to obtain 72.3 mg of white solid, the yield is 93%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0033] like Figure 3 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.0 Hz,2H), 7.91 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 7.9 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 4.02 – 3.94 (m, 2H), 3.93 (s, 3H), 3.16 (d, J = 12.6 Hz, 1H), 2.34 (s, 3H), 2.06 – 1.98 (m, 1H), 0.96 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 199.1, 166.2, 144.9, 139.8, 136.1, 134.0, 129.9, 128.3,128.1, 54.4, 52.6, 46.4, 30.8, 21.7, 20.7, 18.4.HRMS(ESI) m / z: [M+H] + Calcd.For C 21 H 25 O5S: 389.1417, Found 389.1415. Example 4 The γ-carbonyl sulfone derivative provided in Example 4 is 3-(3-Methyl-2-(tosylmethyl)butanoyl)benzonitrile, and the photocatalytic synthesis method thereof comprises the following steps: 3-(2,2-dimethylbut-3-enoyl)benzonitrile (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 15 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and then flash chromatography (V 石油醚 : V 乙酸乙酯 = 6: 1), to obtain 54.0 mg of a white solid with a yield of 76%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0034] like Figure 4 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 8.16 (d, J = 6.6 Hz,2H), 7.85 (d, J = 7.7 Hz, 1H), 7.69 (d, J = 8.1 Hz, 2H), 7.62 (t, J = 8.1 Hz, 1H),7.27 (d, J = 7.9 Hz, 2H), 3.98 (dd, J = 13.2, 10.5 Hz, 1H), 3.91 (dd, J = 10.6, 4.5Hz, 1H), 2.41 (s, 3H), 2.07 – 1.99 (m, 1H), 0.98 (d, J = 6.7 Hz, 3H), 0.81 (d, J = 6.8 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 198.0, 145.1, 137.6, 136.2, 136.1,132.4, 132.1, 130.0, 129.8, 128.1, 117.9, 113.4, 54.8, 46.1, 30.9, 21.7,20.7, 18.6.HRMS(ESI) m / z: [M+H] + Calcd. For C 20 H 22 NO3S: 356.1315, Found356.1318. Example 5 The γ-carbonyl sulfone derivative provided in Example 5 is 3-Methyl-1-( o -tolyl)-2-(tosylmethyl)butan-1-one, and a photocatalytic synthesis method thereof, comprising the following steps: 2,2-Dimethyl-1-(o-tolyl)but-3-en-1-one (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 10 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 45.9 mg of white solid, the yield is 67%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0035] like Figure 5 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.71 (t, J = 7.8 Hz,3H), 7.35 – 7.31 (m, 1H), 7.25 – 7.22 (m, 3H), 7.18 (d, J = 7.6 Hz, 1H), 4.00(dd, J= 13.9, 9.8 Hz, 1H), 3.86 – 3.83 (m, 1H), 3.04 (dd, J = 13.9, 1.2 Hz, 1H), 2.37 (s, 3H), 2.35 (s, 3H), 2.03 – 1.92 (m, 1H), 0.90 (d, J = 6.8 Hz, 3H), 0.70(d, J = 6.9 Hz, 3H). 13 C NMR(101 MHz, CDCl3) δ 202.4, 144.7, 138.8, 137.4, 136.7,132.0, 131.6, 129.9, 128.8, 128.0, 125.9, 53.5, 48.7, 30.2, 21.7, 21.1, 20.8,18.0.HRMS(ESI) m / z: [M+H] + Calcd. For C 20 H 25 O3S: 345.1519, Found 345.1516. Example 6 The γ-carbonyl sulfone derivative provided in Example 6 is 1-(2-Bromophenyl)-3-methyl-2-(tosylmethyl)butan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 1-(2-Bromophenyl)-2,2-dimethylbut-3-en-1-one (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl phenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (1.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 75.1 mg of white solid, the yield is 92%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0036] like Figure 6 As shown, the product NMR characterization:1 H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.2 Hz,2H), 7.70 (dd, J = 7.6, 1.3 Hz, 1H), 7.61 (d, J = 7.9 Hz, 1H), 7.39 (t, J = 7.5 Hz,1H), 7.32 (d, J = 8.0 Hz, 2H), 7.31– 7.27 (m, 1H), 4.04 (dd, J = 13.9, 9.6 Hz,1H), 3.88 – 3.84 (m, 1H), 3.06 (dd, J = 13.9, 1.6 Hz, 1H), 2.41 (s, 3H), 2.13 –2.05 (m, 1H), 0.95 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.9 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 200.7, 144.9, 140.0, 136.8, 134.3, 132.1, 130.0, 129.6, 128.0, 127.5, 120.2, 52.8, 50.0, 29.3, 21.7, 20.7, 17.8.HRMS(ESI) m / z: [M+H] + Calcd.For C 19 H 22 BrO3S: 409.0468, Found 409.0474. Example 7 The γ-carbonyl sulfone derivative provided in Example 7 is 1-(2-Bromo-4-chlorophenyl)-3-methyl-2-(tosylmethyl)butan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 1-(2-bromo-4-chlorophenyl)-2,2-dimethylbut-3-en-1-one (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.002 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl phenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 78.8 mg of white solid, the yield is 89%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0037] like Figure 7 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.2 Hz,2H), 7.70 (d, J = 8.3 Hz, 1H), 7.64 (d, J = 1.7 Hz, 1H), 7.38 (dd, J = 8.3, 1.8 Hz,1H), 7.33 (d, J = 8.0 Hz, 2H), 4.00 (dd, J = 13.9, 9.8 Hz, 1H), 3.84 – 3.81 (m,1H), 3.06 (d, J = 13.8 Hz, 1H), 2.42 (s, 3H), 2.10 – 2.02 (m, 1H), 0.95 (d, J =6.8 Hz, 3H), 0.77 (d, J = 6.9 Hz, 3H). 13C NMR(101 MHz, CDCl3) δ 199.8, 145.0,138.4, 137.6, 136.8, 134.1, 130.6, 130.1, 127.9, 127.8, 121.0, 53.2, 49.9,29.5, 21.7, 20.7, 17.9.HRMS(ESI) m / z: [M+H] + Calcd. For C 19 H 21 BrClO3S: 443.0078,Found 443.0072. Example 8 The γ-carbonyl sulfone derivative provided in Example 8 is 3-Methyl-1-(4-(pyridin-2-yl)phenyl)-2-(tosylmethyl)butan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-(4-(pyridin-2-yl)phenyl)but-3-en-1-one (0.2 mmol), 4-toluenesulfonyl chloride (0.3 mmol), Eosin Y (0.006 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8:1), to obtain 62.0 mg of a white solid with a yield of 76%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0038] like Figure 8 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 8.72 (d, J = 4.5 Hz,1H), 8.07 (d, J = 8.2 Hz, 2H), 7.95 (d, J = 8.3 Hz, 2H), 7.77 (d, J = 3.7 Hz, 2H),7.68 (d, J= 8.0 Hz, 2H), 7.29 – 7.26 (m, 1H), 7.19 (d, J = 7.9 Hz, 2H), 4.04(dd, J = 13.4, 10.1 Hz, 1H), 3.97 (dd, J = 10.3, 4.3 Hz, 1H), 3.17 (d, J = 13.3 Hz,1H), 2.33 (s, 3H), 2.10 – 2.02 (m, 1H), 0.98 (d, J = 6.8 Hz, 3H), 0.78 (d, J =6.8 Hz, 3H). 13 C NMR(101 MHz, CDCl3) δ 199.0, 156.0, 150.0, 144.8, 143.8,137.0, 136.6, 136.2, 129.8, 128.9, 128.2, 127.1, 123.1, 121.1, 54.5, 46.3,31.0, 21.6, 20.7, 18.4.HRMS(ESI) m / z: [M+H] + Calcd. For C 24 H 26 NO3S: 408.1628, Found 408.1625. Example 9 The γ-carbonyl sulfone derivative provided in Example 9 is 3-Methyl-1-phenyl-2-((phenylsulfonyl)methyl)butan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), benzenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.3 mmol), and 4-toluenethiophenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and then flash chromatography (V 石油醚 : V 乙酸乙酯= 8: 1), to obtain 38.1 mg of a white solid with a yield of 60%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0039] like Figure 9 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 7.7 Hz,2H), 7.82 (d, J = 7.5 Hz, 2H), 7.59 – 7.53 (m, 2H), 7.47 – 7.41 (m, 4H), 4.06(dd, J = 13.3, 10.1 Hz, 1H), 3.99 (dd, J = 10.2, 4.2 Hz, 1H), 3.17 (d, J = 13.3 Hz,1H), 2.13 – 2.02 (m, 1H), 1.00 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). 13 CNMR(101 MHz, CDCl3) δ 199.3, 139.3, 136.6, 133.8, 133.4, 129.3, 128.8, 128.5,128.2, 54.3, 46.1, 30.9, 20.8, 18.3.HRMS(ESI) m / z: [M+H] + Calcd. For C 18 H 21 O3S:317.1206, Found 317.1204. Example 10 The γ-carbonyl sulfone derivative provided in Example 10 is 2-(((4-Iodophenyl)sulfonyl)methyl)-3-methyl-1-phenylbutan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), 4-iodobenzenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.5 mmol), and 4-toluenethiophenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 70.4 mg of a white solid with a yield of 80%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0040] like Figure 10 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 7.6 Hz,2H), 7.74 (d, J = 8.4 Hz, 2H), 7.58 (t, J = 7.3 Hz, 1H), 7.49 – 7.45 (m, 4H), 4.04 (dd, J = 13.7, 10.3 Hz, 1H), 3.95 (dd, J = 10.2, 4.4 Hz, 1H), 3.16 (d, J =13.6 Hz, 1H), 2.11 – 2.04 (m, 1H), 1.00 (d, J = 6.8 Hz, 3H), 0.78 (d, J = 6.8 Hz,3H). 13 C NMR(101 MHz, CDCl3) δ 199.1, 138.8, 138.5, 136.3, 133.6, 129.6, 128.8,128.5, 101.9, 54.4, 46.1, 30.9, 20.9, 18.3.HRMS(ESI) m / z: [M+H] + Calcd. ForC 18 H 20IO3S: 443.0172, Found 443.0178. Example 11 The γ-carbonyl sulfone derivative provided in Example 11 is 2-(([1,1'-Biphenyl]-4-ylsulfonyl)methyl)-3-methyl-1-phenylbutan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), 4-phenoxybenzenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenesulfonyl (0.3 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 58.9 mg of a white solid with a yield of 75%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0041] like Figure 11 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.86 (t, J = 8.0 Hz,4H), 7.59 (d, J = 8.4 Hz, 2H), 7.57 – 7.54 (m, 1H), 7.52 (d, J = 7.3 Hz, 2H),7.49 – 7.40 (m, 5H), 4.10 (dd, J = 13.5, 10.3 Hz, 1H), 4.02 (dd, J = 10.1, 4.3Hz, 1H), 3.22 (d, J = 13.6 Hz, 1H), 2.13 – 2.05 (m, 1H), 1.02 (d, J = 6.8 Hz,3H), 0.80 (d, J = 6.8 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 199.2, 146.7, 139.2,137.6, 136.4, 133.4, 129.1, 128.8, 128.8, 128.7, 128.5, 127.8, 127.5, 54.5,46.1, 30.9, 20.9, 18.3.HRMS(ESI) m / z: [M+H] + Calcd. For C 24 H 25 O3S: 393.1519,Found 393.1517. Example 12 The γ-carbonyl sulfone derivative provided in Example 12 is 3-((2-Benzoyl-3-methylbutyl)sulfonyl)benzonitrile, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), 3-cyanobenzenesulfonyl chloride (0.3 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenethiophenol (0.5 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 26.6 mg of white solid, the yield is 39%, and then recrystallized from n-hexane and chloroform to obtain a pure product. The product structure is as follows: .

[0042] like Figure 12 As shown, the product NMR characterization: 1 H NMR(400 MHz, CDCl3) δ 8.04 (s, 1H), 8.02(d, J = 9.0 Hz, 1H), 7.85 (d, J = 7.6 Hz, 2H), 7.79 (d, J = 7.7 Hz, 1H), 7.63 –7.56 (m, 2H), 7.49 (t, J = 7.7 Hz, 2H), 4.08 (dd,J = 13.6, 10.5 Hz, 1H), 4.00(dd, J = 10.4, 3.8 Hz, 1H), 3.22 (d, J = 13.6 Hz, 1H), 2.14 – 2.06 (m, 1H), 1.04(d, J = 6.8 Hz, 3H), 0.78 (d, J = 6.9 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 198.9,141.0, 136.9, 136.0, 134.0, 132.3, 132.0, 130.3, 129.1, 128.4, 116.8, 113.8,54.3, 46.3, 30.9, 20.9, 18.2.HRMS(ESI) m / z: [M+H] + Calcd. For C 19 H 20 NO3S:342.1158, Found 342.1156. Example 13 The γ-carbonyl sulfone derivative provided in Example 13 is 2-(((2-Methoxyphenyl)sulfonyl)methyl)-3-methyl-1-phenylbutan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), 2-methoxybenzenesulfonyl chloride (0.24 mmol), Eosin Y (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenethiophenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography was performed (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 19.4 mg of colorless oil, the yield is 28%, the obtained product structure is as follows: .

[0043] like Figure 13 As shown, the product NMR characterization: 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.7 Hz,2H), 7.72 (d, J = 7.8 Hz, 1H), 7.51 (t, J = 7.4 Hz, 1H), 7.43 (t, J = 7.9 Hz, 1H),7.38 (t, J = 7.7 Hz, 2H), 6.94 (d, J = 8.3 Hz, 1H), 6.82 (t, J = 7.6 Hz, 1H), 4.30(dd, J = 14.1, 10.0 Hz, 1H), 4.00 (s, 3H), 3.85 (dd, J = 10.7, 4.0 Hz, 1H), 3.41(d, J = 14.1 Hz, 1H), 2.06 – 1.98 (m, 1H), 0.95 (d, J = 6.8 Hz, 3H), 0.83 (d, J =6.8 Hz, 3H). 13 C NMR(101 MHz, CDCl3) δ 199.8, 157.7, 136.8, 135.8, 133.2,130.7, 128.6, 128.4, 126.5, 120.4, 112.3, 56.4, 52.8, 46.3, 31.1, 20.7,18.8.HRMS(ESI) m / z: [M+H] + Calcd. For C 19 H 23 O4S: 347.1312, Found 347.1314. Example 14 The γ-carbonyl sulfone derivative provided in Example 14 is 3-Methyl-2-((naphthalen-2-ylsulfonyl)methyl)-1-phenylbutan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), 2-naphthalenesulfonyl chloride (0.36 mmol), EosinY (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenethiophenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The ethyl acetate was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and flash chromatography (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 63.0 mg of white solid, the yield is 86%, the obtained product structure is as follows: .

[0044] like Figure 14 As shown, the product NMR characterization: 1 H NMR(400 MHz, CDCl3) δ 8.30 (s, 1H), 7.92(d, J = 8.7 Hz, 1H), 7.86 (d, J = 8.2 Hz, 1H), 7.80 – 7.74 (m, 4H), 7.64 – 7.60(m, 1H), 7.55 – 7.47 (m, 2H), 7.35 (t, J = 7.7 Hz, 2H), 4.12 (dd, J = 13.7, 10.3Hz, 1H), 4.02 (dd, J = 10.3, 4.5 Hz, 1H), 3.25 (d, J = 13.5 Hz, 1H), 2.12 – 2.01(m, 1H), 1.00 (d, J = 6.8 Hz, 3H), 0.78 (d, J = 6.9 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 199.2, 136.4, 136.0, 135.4, 133.4, 132.1, 130.3, 129.7, 129.4,129.3, 128.7, 128.4, 128.0, 127.7, 122.9, 54.5, 46.2, 31.0, 20.9, 18.4.HRMS(ESI) m / z: [M+H]+ Calcd. For C 22 H 23 O3S: 367.1362, Found 367.1368. Example 15 The γ-carbonyl sulfone derivative provided in Example 15 is 2-((Ethylsulfonyl)methyl)-3-methyl-1-phenylbutan-1-one, and the photocatalytic synthesis method thereof comprises the following steps: 2,2-Dimethyl-1-phenylbut-3-ene-1-one (0.2 mmol), ethylsulfonyl chloride (0.3 mmol), EosinY (0.004 mmol), Na3PO4 (0.4 mmol), and 4-toluenethiophenol (0.4 mmol) were added to a 10 mL light-transmitting screw-capped bottle. After adding the reaction solvent hexafluoroisopropanol (2.0 mL), the air was replaced with argon and the bottle was sealed. The bottle was placed under 20 W blue light and stirred for 12 h. After the reaction was complete, an aqueous solution was added to quench the reaction and the solution was extracted with ethyl acetate three times. The organic phase was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure and then flash column chromatography (V 石油醚 : V 乙酸乙酯 = 8: 1), to obtain 40.8 mg of white solid, the yield is 76%, the obtained product structure is as follows: .

[0045] like Figure 15 As shown, the product NMR characterization: 1 H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 7.5 Hz,2H), 7.59 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.7 Hz, 2H), 4.05 (dd, J = 11.0, 3.7Hz, 1H), 3.94 (dd, J = 13.8, 10.4 Hz, 1H), 2.97 (d, J = 13.7 Hz, 1H), 2.94 – 2.84(m, 2H), 2.19 – 2.11 (m, 1H), 1.37 (t, J = 7.4 Hz, 3H), 1.05 (d, J = 6.8 Hz, 3H),0.81 (d, J = 6.9 Hz, 3H).13 C NMR(101 MHz, CDCl3) δ 200.5, 136.6, 133.7, 129.0,128.7, 49.8, 48.7, 46.3, 30.8, 20.9, 18.3, 6.7.HRMS(ESI) m / z: [M+H] + Calcd.For C 14 H 21 O3S: 269.1206, Found 269.1200。

Claims

1. A photocatalytic synthesis method of γ-carbonyl sulfone derivatives, characterized in that: The following steps are involved: Adding a β,γ-unsaturated ketone compound, a sulfonyl chloride compound, a photocatalyst, a base and an additive into a solvent, performing a photocatalytic reaction, and then separating and purifying to obtain a γ-carbonyl sulfone derivative as shown in formula (I); Among them, R 1 is selected from hydrogen, alkyl, trifluoromethoxy, halogen, ester, cyano or heterocycle; R 2 is selected from hydrogen, alkyl, phenyl, methoxy, halogen, cyano or fused ring.

2. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 1, characterized in that: The general structural formula of the β,γ-unsaturated ketone compound is shown in Formula (II): Among them, R 1 is selected from hydrogen, alkyl, trifluoromethoxy, halogen, ester, cyano or heterocycle.

3. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 2, characterized in that: The β,γ-unsaturated ketone compound is selected from 2,2-dimethyl-1-phenylbut-3-ene-1-one, 2,2-dimethyl-1-(4-(trifluoromethoxy)phenyl)but-3-ene-1-one, 4-(2,2-dimethylbut-3-enoyl)benzoic acid methyl ester, 3-(2,2-dimethylbut-3-enoyl)benzonitrile, 2,2-dimethyl-1-(o-tolyl)but-3-ene-1-one, 1-(2-bromophenyl)-2,2-dimethylbut-3-ene-1-one, 1-(2-bromo-4-chlorophenyl)-2,2-dimethylbut-3-ene-1-one or 2,2-dimethyl-1-(4-(pyridin-2-yl)phenyl)but-3-ene-1-one.

4. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 1, characterized in that: The general structural formula of the sulfonyl chloride compound is shown in formula (III): Among them, R 2 is selected from hydrogen, alkyl, phenyl, methoxy, halogen, cyano or fused ring.

5. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 4, characterized in that: The sulfonyl chloride compound is selected from one of 4-toluenesulfonyl chloride, benzenesulfonyl chloride, 4-iodobenzenesulfonyl chloride, 4-phenoxybenzenesulfonyl chloride, 3-cyanobenzenesulfonyl chloride, 2-methoxybenzenesulfonyl chloride, 2-naphthalenesulfonyl chloride and ethylsulfonyl chloride.

6. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 1, characterized in that: The molar ratio of the β,γ-unsaturated ketone compound to the sulfonyl chloride compound is 1.0: (1.2-1.8).

7. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 1, characterized in that: The photocatalyst is Eosin Y, and the molar ratio of Eosin Y to the β,γ-unsaturated ketone compound is (0.01-0.03):1.0; the base is Na3PO4, and the molar ratio of Na3PO4 to the β,γ-unsaturated ketone compound is (1.5-2.5):1; the additive is 4-toluenethiophenol, and the molar ratio of 4-toluenethiophenol to the β,γ-unsaturated ketone compound is (1.5-2.5):1; the solvent is hexafluoroisopropanol, isopropanol or dimethyl sulfoxide, and the ratio of the volume of the solvent to the molar amount of the β,γ-unsaturated ketone compound is (0.5-1) mL:0.1 mmol.

8. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 1, characterized in that: The conditions for the photocatalytic reaction are: stirring for 10 to 15 hours under 15 to 30 W blue LED irradiation at room temperature.

9. The photocatalytic synthesis method of γ-carbonyl sulfone derivatives according to claim 1, characterized in that: The separation and purification conditions are as follows: after the photocatalytic reaction, deionized water is first added to quench the reaction, followed by extraction with ethyl acetate 2 to 4 times, the ethyl acetate is collected and dried over anhydrous sodium sulfate, filtered, reduced pressure, and then subjected to flash chromatography to finally obtain γ-carbonyl sulfone derivatives.

10. A γ-carbonyl sulfone derivative, characterized in that: The invention is synthesized by the photocatalytic synthesis method of the gamma-carbonyl sulfone derivatives according to any one of claims 1 to 9.

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