A method for preparing allyl sulfone compounds by using visible light assisted cobalt catalysis

Abstract

The present invention is a method for preparing allyl sulfone compounds by visible light synergistic cobalt catalysis, comprising adding cyclobutanone oxime ester, α-methylstyrene, 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO), inorganic base, dibutyl diketoximine pyridine cobalt chloride (Co(dmgH)2PyCl) to dimethyl sulfoxide (DMSO) solvent to obtain a mixed solution, and irradiating the mixed solution with 450 nanometer LED light at room temperature and in an inert gas atmosphere. The present invention does not require the use of sulfonyl reagents and photocatalysts, only uses cheap metals as catalysts, and can achieve gram-level reactions by visible light irradiation at room temperature, with the advantages of high efficiency, conservation and environmental protection. Moreover, the reaction conditions of the present invention are mild, the raw materials are simple and easy to obtain, and it is safe and easy to operate in industrial production, and has great potential for large-scale application value.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic synthesis and relates to a method for preparing allyl sulfone compounds by catalysis assisted by visible light and cobalt. Background Art

[0002] Allyl sulfone is a very important sulfur-containing compound, and its structural fragments are widely present in biologically active molecules and drug molecules. For example, drug molecules containing sulfone groups, such as linezolid (thiapyran sulfone), tazobactam (-)-agelasidine A, are mostly used to inhibit the growth of fungi and have good antibacterial effects. Dorzolamide (dorzolamide-HCl) is a good drug for the treatment of glaucoma. The allyl sulfone skeleton structure is also used as a synthon and is widely used in the synthesis and modification of drug molecules and functional materials. In view of the importance of allyl sulfone compounds, many synthetic researchers have done a lot of research work on this in the past decade, with the goal of developing a greener, more efficient and highly selective synthesis method. So far, the synthesis methods of allyl sulfone compounds can be roughly divided into two types: traditional oxidation type and cross-coupling type.

[0003] Traditional oxidation strategy: The traditional oxidation strategy for synthesizing allyl sulfone generally uses allyl sulfide as a substrate, and uses hydrogen peroxide, nitric acid, manganese dioxide, periodic acid, chromium trioxide and oxygen oxidants to oxidize the sulfur group to a sulfone group under certain conditions.

[0004] At present, the synthesis methods of allyl sulfone are mostly limited to specific raw materials such as thioether / allyl alcohol / amine / carbonate and propargylamine, and require the participation of strong oxidants and the use of precious metal catalysis, which reduces the reaction efficiency and increases the reaction cost. More importantly, the sulfur sources used in the reaction are all existing organic sulfur sources such as benzenesulfinate and benzenesulfonylhydrazide, which are very limited in variety and cannot meet the diverse needs of allyl sulfone synthesis. Summary of the invention

[0005] The invention provides a simple, efficient and green method for constructing allyl sulfone compounds, which utilizes visible light in coordination with cobalt catalysis, adopts sulfur dioxide as a sulfur source, uses cheap and readily available α-methylarylethylene and cyclobutanone oxime ester as raw materials, and uses dibutyl dione oxime pyridine cobalt chloride as a catalyst, and utilizes photoreaction to construct allyl sulfone groups, thereby solving the problem that traditional methodologies are limited to specific raw materials for constructing allyl sulfone compounds.

[0006] A method for preparing allyl sulfone compounds by cobalt catalysis assisted by visible light mainly comprises α-Methylstyrene, cyclobutanone oxime ester compound, inorganic base, 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO), and dibutyl diketoximine pyridine cobalt chloride (Co(dmgH)2PyCl) are added to a solvent to obtain a mixed solution. The mixed solution is irradiated with visible light at room temperature and inert gas atmosphere to obtain an allyl sulfone compound.

[0007] The inorganic base can be potassium carbonate, sodium bicarbonate, etc.

[0008] The reaction path of the preparation method of the present invention is: 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO) is converted into triethylenediamine (DABCO) in an organic reaction solution and sulfur dioxide (SO2) is released; cyclobutanone oxime ester and DABCO form an EDA (electron donor and acceptor) complex under the action of potassium carbonate, and react under light conditions to generate a butyronitrile free radical a, which is converted into a butyronitrile sulfonyl free radical b by adding SO2; the sulfonyl free radical is converted into a butyronitrile sulfonyl free radical b by adding SO2; α -methylstyrene generates benzylic free radical c. The metal catalyst Co(dmgH)2PyCl (hereinafter referred to as Co(Ⅲ)) is excited by light under the irradiation of 450 nm wavelength blue LED light to reach the excited state Co * (III) The excited cobaloxime oxidizes DABCO to convert it into Co(II) and releases H + Then Co(II) is inserted into c to convert into Co(III)-C intermediate d, which finally undergoes β-H elimination reaction to generate product-1 and Co(III)-H species. Co(III)-H reacts with H + Combined to generate hydrogen and return to the initial state Co(III) to complete the catalytic cycle.

[0009] Furthermore, the α- The structural formula of methyl styrene is as follows:

[0010]

[0011] In the formula, R1, R2, R3, R4, and R5 are all H; or one of R2, R3, and R4 is CH3, and the others are all H; or R3 is Et, and the others are all H; or R3 is i Pr, the rest are all H; or R3 is tBu, and the rest are all H; or R3 is Amyl, and the rest are all H; or R3 is Cy, and the rest are all H; or R2 is OCF3, and the rest are all H; or one of R2, R3, and R5 is F, and the rest are all H; or one of R2, R3, and R5 is Cl, and the rest are all H; or one of R2 and R3 is CF3, and the rest are all H; or R3 is CN, and the rest are all H; or R2 and R3 are CH3CO, and the rest are all H; or R2 and R3 are CH3O2C, and the rest are all H; or R2 is TsNH, and the rest are all H; or R2 is BocNH, and the rest are all H; or R3 is CH2OH, and the rest are all H; or R3 is TMS, and the rest are all H.

[0012] Further, the structural formula of the cyclobutanone oxime ester is:

[0013] ;

[0014] Wherein, R1, R2, and R3 are all H; or R1 is n Bu, the rest are all H; or R1 is PhCH2CH2, the rest are all H; or R1 is n-octyl, the rest are all H; or R1 is n-hexadecyl, the rest are all H; or R1 is CH2=CHCH2, the rest are all H; or R1 is CH3OCH2CH2, the rest are all H; or R2 is n Bu, the rest are H; or R2 is Ph, the rest are H; or R2 is p - t BuPh, the rest are all H; or R2 is t BuOCO, and the rest are all H; or R2 is BnO, and the rest are all H; or R2 is BnOCH2, and the rest are all H; R2 is 2-naphthyl, and the rest are all H; or R2 is CH3, R3 is Ph, and the rest are all H.

[0015] Furthermore, the solvent is dimethyl sulfoxide.

[0016] Furthermore, the ratio of the cyclobutanone oxime ester to the solvent is 0.08-0.10 mmol:1 mL; the ratio of the α-methylstyrene to the solvent is 0.24-0.30 mmol:1 mL; the ratio of the DABSO to the solvent is 0.12-0.15 mmol:1 mL; and the ratio of the Co(dmgH)2PyCl to the solvent is 3.0-4.0 mg:1 mL.

[0017] Furthermore, the visible light irradiation is performed using blue LEDs with a wavelength of 450nm±10nm, the irradiation temperature is room temperature, and the irradiation time is 8-10h.

[0018] Furthermore, the structural formula of the allyl sulfone compound is as follows:

[0019]

[0020] In the formula, R1, R2, R3, R4, R5, R6, R7, R8 are all H; or R3 is CH3, and the rest are all H; or R3 is Et, and the rest are all H; or R3 is i Pr, the rest are all H; or R3 is t Bu, and the rest are all H; or R3 is Amyl, and the rest are all H; or R3 is Cy, and the rest are all H; or R3 is OCF3, and the rest are all H; the rest are all H; or one of R2, R3, and R5 is F, and the rest are all H; or one of R2, R3, and R5 is Cl, and the rest are all H; or one of R2 and R3 is CF3, and the rest are all H; or R3 is CN, and the rest are all H; or R2 and R3 are CH3CO, and the rest are all H; or R2 and R3 are CH3O2C, and the rest are all H; or R2 is TsNH, and the rest are all H; or R2 is BocNH, and the rest are all H; or R3 is CH2OH, and the rest are all H; or R3 is TMS, and the rest are all H; or R6 is n Bu, and the rest are all H; or R6 is PhCH2CH2, and the rest are all H; or R6 is n-octyl, and the rest are all H; or R6 is n-hexadecyl, and the rest are all H; or R6 is CH2=CHCH2, and the rest are all H; or R6 is CH3OCH2CH2, and the rest are all H; or R7 is n Bu, and the rest are all H; or R7 is Ph, and the rest are all H; or R7 is p - t BuPh, the rest are all H; or R7 is t BuOCO, and the rest are all H; or R7 is BnO, and the rest are all H; or R7 is BnOCH2, and the rest are all H; or R7 is 2-naphthyl, and the rest are all H; or R7 is CH3, R8 is Ph, and the rest are all H.

[0021] Compared with the prior art, the present invention uses a simple, efficient, green and safe method to construct allyl sulfone compounds, which mainly has the following advantages:

[0022] (1) The reaction system of the present invention is simple and easy to operate. The reaction of the present invention can achieve the construction of allyl sulfone compounds by irradiating with visible light at room temperature and in an inert gas atmosphere, without the need for harsh reaction conditions such as heating and pressurization. The reaction device is simple and easy to achieve industrial production.

[0023] (2) Different from the previous synthesis methods of allyl sulfone compounds, the present invention uses sulfur dioxide as a sulfur source to directly construct the sulfone group in the reaction, rather than using existing sulfone compounds as a sulfur source. Since the types of existing commercial sulfone compounds are relatively limited, using them as a sulfur source will result in a relatively single type of product. However, the present invention uses sulfur dioxide as a sulfur source, and can form a variety of sulfonyl groups through different types of alkyl free radicals combined with sulfur dioxide, making the synthesized allyl sulfone compounds more diverse.

[0024] (3) The preparation cost of the present invention is low. The raw materials used in the catalytic system of the present invention are simple, cheap, and easily available commercial compounds. The reaction substrates have good universality, and the entire reaction system is economical and efficient. For example, although the reaction is achieved in the form of photochemistry, there is no need to add a photocatalyst. The metal catalyst used is a very cheap cobalt catalyst reagent, and the reaction only requires a catalytic amount of cobalt metal reagent to efficiently achieve the synthesis of allyl sulfone, which greatly saves the cost of the reaction; the raw material 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO) used in the reaction is not only a source of sulfur dioxide, but the triethylenediamine (DABCO) released by it can also participate in the reaction as an electron donor, which effectively improves the utilization efficiency of the raw materials. Other sulfur dioxide sources such as pyrosulfite, sodium bisulfite, etc. cannot achieve this reaction goal because these sulfur sources can only provide sulfur dioxide but cannot serve as electron donors.

[0025] (4) The preparation method of the present invention is green and environmentally friendly. The present invention uses low-toxic cobalt metal as a catalyst and does not need to use highly toxic metal photocatalysts, which avoids the problem of toxic metal residues in the product. The reaction can be caused by 450nm blue LED light, avoiding large energy consumption. The reaction can also generate high-value-added hydrogen, which is very consistent with the concept of green chemistry; it can also achieve gram-level reactions, and has good yields, green and efficient, and environmentally friendly advantages, and has potential application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a reaction flow chart of the preparation of allyl sulfone compounds by visible light synergistic cobalt catalysis of the present invention;

[0027] Figure 2 This is a reaction mechanism diagram of the preparation of allyl sulfone compounds by visible light synergistic cobalt catalysis of the present invention;

[0028] Figure 3 is the H NMR spectrum of the 4-((2-phenylallyl)sulfonyl)butyronitrile compound prepared in Example 1;

[0029] Figure 4is the carbon spectrum of the 4-((2-phenylallyl)sulfonyl)butyronitrile compound prepared in Example 1;

[0030] Figure 5 is the mass spectrum of the 4-((2-phenylallyl)sulfonyl)butyronitrile compound prepared in Example 1;

[0031] Figure 6 This is a physical picture of the 4-((2-phenylallyl)sulfonyl)butyronitrile compound prepared in Example 1. DETAILED DESCRIPTION

[0032] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings.

[0033] Example 1

[0034] In the reaction flask, 0.20 mmol of cyclobutanone oxime ester compound, 0.6 mmol α- Methylstyrene compound, 0.20mmol potassium carbonate and 0.20mmol DABSO were dissolved in 2mL dimethyl sulfoxide to obtain a dimethyl sulfoxide solution; Co(dmgH)2PyCl (bis(dimethylglyoxime)pyridine cobalt chloride) was used as a metal catalyst, and 8.0mg of the catalyst was added to the dimethyl sulfoxide solution; the reaction bottle was purged with nitrogen for 10min to remove oxygen, and then illuminated with a 450nm wavelength blue LED lamp at room temperature for 10h under stirring with a magnetic stirrer. After the reaction was completed, 50mL of water was added to the reaction, and the mixed aqueous phase was extracted with ethyl acetate (3×15.0mL), the combined organic phases were washed with 50mL of water, and then dried over Na2SO4, evaporated and concentrated under reduced pressure, and the concentrated solution was separated and purified by column chromatography (n-hexane / ethyl acetate = 1 / 1) to obtain an allyl sulfone compound. By nuclear magnetic hydrogen spectrum, carbon spectrum, and mass spectrum such as Figure 3 , Figure 4 and Figure 5 , identified as 4-((2-phenylallyl)sulfonyl)butyronitrile. The yield of the product was 82%.

[0035] 1 H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 6.6 Hz, 2H), 7.43–7.28 (m, 3H), 5.77 (s, 1H), 5.57 (s, 1H), 4.20 (s, 2H), 2.93 (t, J = 7.3 Hz, 2H), 2.46 (t, J =7.0 Hz, 2H), 2.08 (p, J= 7.2 Hz, 2H).

[0036] 13 C NMR (101 MHz, CDCl3) δ 138.6, 136.0, 128.9, 128.8, 126.3, 122.6,118.1, 59.69, 50.0, 18.1, 16.2.

[0037] HRMS(ESI) calculated for C 13 H 19 N2O2S + [M+ NH4] + 267.1162, found:267.1159.

[0038] Example 2

[0039] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-2 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is CH3). The yield of the product is 87%.

[0040] Example 3

[0041] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-3 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is Et). The yield of the product is 82%.

[0042] Example 4

[0043] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-4 (R1, R2, R4, R5, R6, R7, R8, are H, R3 is i Pr). The yield of the product is 85%.

[0044] Example 5

[0045] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-5 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is tBu). The yield of the product is 90%.

[0046] Example 6

[0047] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-6 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is n-pentyl). The yield of the product is 81%.

[0048] Example 7

[0049] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-7 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is Cy). The yield of the product is 88%.

[0050] Example 8

[0051] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-8 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is CH3). The yield of the product is 81%.

[0052] Example 9

[0053] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-9 (R1, R3, R4, R5, R6, R7, R8, are H, and R2 is OCH3). The yield of the product is 85%.

[0054] Example 10

[0055] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-10 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is F). The yield of the product is 76%.

[0056] Embodiment 11

[0057] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-11 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is Cl). The yield of the product is 83%.

[0058] Example 12

[0059] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-12 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is CF3). The yield of the product is 60%.

[0060] Embodiment 13

[0061] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-13 (R1, R3, R5, R6, R7, R8, are H, R2, R4 are F). The yield of the product is 77%.

[0062] Embodiment 14

[0063] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-14 (R1, R3, R4, R5, R6, R7, R8, are H, and R2 is CF3). The yield of the product is 68%.

[0064] Embodiment 15

[0065] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-15 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is OCF3). The yield of the product is 85%.

[0066] Example 16

[0067] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-16 (R1, R3, R4, R5, R6, R7, R8, are H, and R2 is CH3CO). The yield of the product is 76%.

[0068] Embodiment 17

[0069] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-17 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is CH3CO). The yield of the product is 68%.

[0070] Embodiment 18

[0071] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-18 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is CN). The yield of the product is 62%.

[0072] Embodiment 19

[0073] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-19 (R1, R 2、 R4, R5, R6, R7, R8, are H, and R3 is CO2Me). The yield of the product is 65%.

[0074] Embodiment 20

[0075] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-20 (R1, R3, R4, R5, R6, R7, R8, are H, and R2 is CO2Me). The yield of the product is 72%.

[0076] Embodiment 21

[0077] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-21 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is CH2OH). The yield of the product is 64%.

[0078] Embodiment 22

[0079] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-22 (R1, R3, R4, R5, R6, R7, R8, are H, and R2 is TsNH). The yield of the product is 67%.

[0080] Embodiment 23

[0081] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-23 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is BocNH). The yield of the product is 63%.

[0082] Embodiment 24

[0083] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-24 (R1, R2, R4, R5, R6, R7, R8, are H, and R3 is TMS). The yield of the product is 65%.

[0084] Embodiment 25

[0085] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-25 (R1, R2, R3, R4, R5, R7, R8, are H, R6 is n Bu). The yield of the product is 83%.

[0086] Embodiment 26

[0087] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-26 (R1, R2, R3, R4, R5, R7, R8, are H, and R6 is PhCH2CH2). The yield of the product is 68%.

[0088] Embodiment 27

[0089] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-27 (R1, R2, R3, R4, R5, R7, R8, are H, and R6 is n-octyl). The yield of the product is 76%.

[0090] Embodiment 28

[0091] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-28 ((R1, R2, R3, R4, R5, R7, R8, are H, R6 is n-hexadecyl). The yield of the product is 83%.

[0092] Embodiment 29

[0093] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-29 ((R1, R2, R3, R4, R5, R7, R8, are H, R6 is CH2=CHCH2). The yield of the product is 87%.

[0094] Embodiment 30

[0095] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-30 ((R1, R2, R3, R4, R5, R7, R8, are H, R6 is CH3OCH2CH2). The yield of the product is 90%.

[0096] Embodiment 31

[0097] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-31 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is n Bu). The yield of the product is 82%.

[0098] Embodiment 32

[0099] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-32 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is Ph). The yield of the product is 83%.

[0100] Embodiment 33

[0101] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-33 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is p - t BuPh). The yield of the product is 80%.

[0102] Embodiment 34

[0103] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-34 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is t The yield of the product was 62%.

[0104] Embodiment 35

[0105] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-35 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is BnO). The yield of the product is 90%.

[0106] Embodiment 36

[0107] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-36 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is BnOCH2). The yield of the product is 72%.

[0108] Embodiment 37

[0109] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-37 ((R1, R2, R3, R4, R5, R6, R8, are H, R7 is 2-naphthyl). The yield of the product is 79%.

[0110] Embodiment 38

[0111] Same as Example 1, except that the product is 4-((2-phenylallyl)sulfonyl)butyronitrile product-38 ((R1, R2, R3, R4, R5, R6, are H, R7 is CH3, R8 is Ph). The yield of the product is 87%.

[0112] Embodiment 39

[0113] The potassium carbonate in Example 1 was replaced by sodium bicarbonate, and the other conditions and steps remained unchanged, and the yield of the product was 78%.

[0114] The Co(dmgH)2PyCl (bis(dimethylglyoximepyridine)cobalt chloride) in Example 1 was replaced with bis(cyclohexanedione)oximepyridine)cobalt chloride, and other conditions and steps remained unchanged, and the yield of the product was 80%.

[0115] The Co(dmgH)2PyCl (bis(dimethylglyoxime pyridine) cobalt chloride) in Example 1 was replaced with bis(cyclohexanedione oxime bipyridine) cobalt hexafluorophosphate, and other conditions and steps remained unchanged, and the product yield was 76%.

[0116] The Co(dmgH)2PyCl (bis(dimethylglyoxime)pyridine cobalt chloride) in Example 1 was replaced with bis(cyclohexanedione)oxime cobalt dichloride, and other conditions and steps remained unchanged, and the product yield was 78%.

[0117] In Example 1 α-When the amount of methylstyrene was replaced with 5 times the equivalent of cyclobutanone oxime ester, the other conditions and steps remained unchanged, and the yield of the product was 80%.

[0118] When the amount of 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO) in Example 1 was replaced with 3 times the equivalent of cyclobutanone oxime ester, the other conditions and steps remained unchanged, and the yield of the product was 75%.

[0119] When the amount of potassium carbonate in Example 1 was replaced with twice the equivalent of cyclobutanone oxime ester, the other conditions and steps remained unchanged, and the yield of the product was 78%.

[0120] When the amount of Co(dmgH)2PyCl (bis(dimethylglyoxime)pyridine cobalt chloride) in Example 1 was replaced with 0.2 equivalents of cyclobutanone oxime ester, the other conditions and steps remained unchanged, and the yield of the product was 80%.

[0121] Comparative Example 1

[0122] The dimethyl sulfoxide (DMSO) in Example 1 was replaced with 1,2-dichloroethane (DCE), and other conditions and steps remained unchanged, and the yield of the product was 56%.

[0123] The dimethyl sulfoxide (DMSO) in Example 1 was replaced by acetonitrile (ACN), and other conditions and steps remained unchanged, and the yield of the product was 75%.

[0124] The dimethyl sulfoxide (DMSO) in Example 1 was replaced by acetone, and the other conditions and steps remained unchanged, and the yield of the product was 72%.

[0125] The dimethyl sulfoxide (DMSO) in Example 1 was replaced by N,N -dimethylformamide (DMF), other conditions and steps remained unchanged, and the yield of the product was 70%.

[0126] The potassium carbonate in Example 1 was replaced by triethylenediamine (DABCO), and the other conditions and steps remained unchanged, and the yield of the product was 76%.

[0127] The potassium carbonate in Example 1 was replaced by pyridine, and the other conditions and steps remained unchanged, and the yield of the product was 32%.

[0128] The potassium carbonate in Example 1 was replaced by potassium phosphate, and the other conditions and steps remained unchanged, and the yield of the product was 45%.

[0129] Comparative Example 2

[0130] The target product could not be obtained by replacing 1,4-diazabicyclo[2.2.2]octane-1,4-diamium-1,4-disulfinic acid (DABSO) in Example 1 with sodium pyrosulfite while other conditions and steps remained unchanged.

[0131] The target product could not be obtained by replacing 1,4-diazabicyclo[2.2.2]octane-1,4-diamium-1,4-disulfinic acid (DABSO) in Example 1 with sodium bisulfite, while other conditions and steps remained unchanged.

[0132] The target product could not be obtained by replacing cyclobutanone oxime ester and 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO) in Example 1 with p-toluenesulfonyl hydrazide while other conditions and steps remained unchanged.

[0133] In Example 1 α- When methylstyrene was replaced by p-methoxystyrene and other conditions and steps remained unchanged, the target product could not be obtained.

[0134] In Example 1 α- When methylstyrene was replaced by 1,1-diphenylethylene and other conditions and steps remained unchanged, the target product could not be obtained.

Claims

1. A method for preparing allyl sulfone compounds by using visible light and cobalt catalysis, characterized in that: The method comprises adding cyclobutanone oxime ester, α-methylstyrene, 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid, an inorganic base, and dibutyl diketoximine pyridine cobalt chloride into a solvent to obtain a mixed solution, deoxygenating the mixed solution with an inert gas, and then irradiating the mixed solution with visible light at room temperature and in an inert gas atmosphere; The structural formula of the α-methylstyrene is as follows: ； The structural formula of the cyclobutanone oxime ester is: ； The structural formula of the allyl sulfone compound is as follows: ； In the formula, R1, R2, R3, R4, R5, R6, R7, and R8 are all H; or R3 is CH3, and the rest are all H; or R3 is Et, and the rest are all H; or R3 is i Pr, the rest are all H; or R3 is t Bu, and the rest are all H; or R3 is Amyl, and the rest are all H; or R3 is Cy, and the rest are all H; or R3 is OCF3, and the rest are all H; or one of R2, R3, and R5 is F, and the rest are all H; or one of R2, R3, and R5 is Cl, and the rest are all H; or one of R2 and R3 is CF3, and the rest are all H; or R3 is CN, and the rest are all H; or R2 and R3 are CH3CO, and the rest are all H; or R2 is CH3O2C, and the rest are all H; or R2 is TsNH, and the rest are all H; or R2 is BocNH, and the rest are all H; or R3 is CH2OH, and the rest are all H; or R3 is TMS, and the rest are all H; or R6 is n Bu, and the rest are all H; or R6 is PhCH2CH2, and the rest are all H; or R6 is n-octyl, and the rest are all H; or R6 is n-hexadecyl, and the rest are all H; or R6 is CH2=CHCH2, and the rest are all H; or R6 is CH3OCH2CH2, and the rest are all H; or R7 is n Bu, and the rest are all H; or R7 is Ph, and the rest are all H; or R7 is p- t BuPh, the rest are all H; or R7 is t BuOCO, and the rest are all H; or R7 is BnO, and the rest are all H; or R7 is BnOCH2, and the rest are all H; or R7 is 2-naphthyl, and the rest are all H; or R7 is CH3, R8 is Ph, and the rest are all H; R1, R2, R3, R4, and R5 in the structural formula of the α-methylstyrene correspond one-to-one to R1, R2, R3, R4, and R5 in the structural formula of the allyl sulfone compound; R6, R7, and R8 in the structural formula of the cyclobutanone oxime ester correspond one-to-one to R6, R7, and R8 in the structural formula of the allyl sulfone compound; The solvent is dimethyl sulfoxide; The inorganic base is potassium carbonate or sodium bicarbonate.

2. The method according to claim 1, characterized in that: The ratio of the cyclobutanone oxime ester to the solvent is 0.08-0.10 mmol:1 mL; the ratio of the α-methylstyrene to the solvent is 0.24-0.30 mmol:1 mL; the ratio of the 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid to the solvent is 0.12-0.15 mmol:1 mL; the ratio of the bis(dimethylglyoxime)pyridine cobalt chloride to the solvent is 3.0-4.0 mg:1 mL.

3. The method according to claim 1, characterized in that: The visible light irradiation is performed by using a blue LED light with a wavelength of 450nm±10nm, the irradiation temperature is room temperature, and the irradiation time is 8-10h.

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