Synthesis method of novel alpha, beta-unsaturated ketone

Abstract

The invention discloses a synthesis method of novel alpha, beta-unsaturated ketone, which comprises the following steps: by taking aryl acyl chloride and olefin as raw materials, catalyzing the aryl acyl chloride through light-induced copper to generate acyl free radicals, and then carrying out free radical addition reaction and elimination on the acyl free radicals and the olefin, so as to efficiently construct an alpha, beta-unsaturated ketone compound. Compared with an existing method depending on an expensive iridium catalyst or organic dye, the method has the advantages that the cheap and high-yield copper catalyst is directly adopted, the production cost is remarkably reduced, and the economic benefit is improved. The method has the characteristics of mild reaction conditions, easily available catalyst and raw materials, use of clean and sustainable light energy as driving force, simplicity and convenience in operation and the like. The invention provides a new way which is economical, environment-friendly and easy for large-scale production for the synthesis of the alpha, beta-unsaturated ketone compound.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a novel synthesis method of α, β-unsaturated ketone. Background Art

[0002] α,β-Unsaturated ketones are the core structural skeletons of many natural compounds and are widely distributed in vegetables, fruits, teas, and other plants. They have attracted great interest due to their wide range of biological activities, including anticancer activity, cancer prevention, anti-inflammatory activity, antibacterial activity, etc. For example, metochalcone was once marketed as a choleretic drug, while sofalcone was once used as an anti-ulcer and mucosal protective drug. Therefore, it is of great significance to develop new green general synthetic methods to obtain such compounds.

[0003] Traditionally, the synthesis of α,β-unsaturated ketones mainly uses the Claisen-Schmidt reaction, but this method often leads to the formation of complex mixtures, which makes it difficult to purify α,β-unsaturated ketones. In recent years, emerging cross-coupling strategies such as cross-metathesis, transition metal-catalyzed alkyne hydroacylation, copper-catalyzed condensation cross-coupling, palladium-catalyzed carbonylation, and nitrogen heterocyclic carbene-catalyzed carbonylation have been further developed. However, these methods usually require harsh reaction conditions or the use of expensive metal catalysts. In addition, although photoredox methods have also made progress, they still rely on the very expensive photocatalyst fac-Ir(ppy)3, which makes the practical application of such reactions out of reach, especially for large-scale production. Therefore, the development of a mild, low-cost, light-induced, inexpensive metal-catalyzed method for the synthesis of α,β-unsaturated ketones is of great significance and research value in synthetic chemistry and industrial production. Summary of the invention

[0004] The technical problem to be solved by the invention is to develop a mild and inexpensive method for synthesizing α,β-unsaturated ketones from aryl acyl chlorides and olefins catalyzed by light-induced copper.

[0005] To solve the above technical problems, the present invention adopts the following technical scheme: a novel method for synthesizing α,β-unsaturated ketones, which uses aryl acyl chloride and olefin as raw materials, generates acyl radicals by photoinduced copper catalysis of aryl acyl chloride, and then undergoes free radical addition reaction with olefin to obtain α,β-unsaturated ketone compounds.

[0006] This method conforms to the following reaction equation:

[0007]

[0008] Aryl acid chloride Olefin derivatives are Among them, R1 represents an alkyl group, an alkoxy group, a phenyl group, a halogen group, etc. containing one or more substitutions; R 2 represents a hydrogen atom or an alkyl group containing one or more substitutions; R 3 represents a hydrogen atom or an alkyl group or a phenyl group containing one or more substitutions; R 4 It means an alkyl group, an alkoxy group, a phenyl group, a halogen group, etc. containing one or more substitutions.

[0009] The copper catalyst is one or a mixture of two or more of CuCl, CuBr, CuI, Cu2O and CuO.

[0010] The synthesis method of the above-mentioned α, β-unsaturated ketone compound is operated according to the following steps: in a reaction tube, an olefin derivative, an aromatic acid chloride, a copper catalyst, a ligand, a base and a solvent are added, and the reaction is stirred for 6 hours under N2 protection and light irradiation. After the reaction is completed, DBU is added and the reaction is stirred at room temperature in the air for 30 minutes, and the crude product is filtered and the solvent is removed under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain an α, β-unsaturated ketone compound.

[0011] The light is 450nm wavelength blue light or sunlight.

[0012] The molar ratio of the aryl acid chloride to the olefin derivative is 3:2.

[0013] The ligand is 1,1'-binaphthyl-2,2'-bis(diphenylphosphine) (BINAP).

[0014] The base is one or a mixture of two or more of lithium carbonate, potassium dihydrogen phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, and 2,6-di-tert-butyl-4-methylpyridine.

[0015] The solvent is one or a mixture of two or more of tetrahydrofuran, fluorobenzene, trifluorotoluene, 1,4-dioxane, N,N-dimethylacetamide, cyclopentyl methyl ether, 2-methyltetrahydrofuran, dichloroethane and acetonitrile.

[0016] The reaction tube is a quartz tube or a glass tube.

[0017] The eluent in the column chromatography is petroleum ether or a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of (20-100):1.

[0018] In view of the problems existing in the current synthesis of α,β-unsaturated ketones, the inventors have established a method for synthesizing α,β-unsaturated ketone compounds, using olefin derivatives and aryl acyl chlorides as raw materials, and realizing the free radical addition reaction of aryl acyl chlorides and olefin derivatives through photoinduced copper catalysis to obtain α,β-unsaturated ketone compounds. Among them, the direct use of clean and sustainable light energy greatly improves energy efficiency and reduces process costs; compared with commonly used iridium and ruthenium photocatalysts, copper reserves are more abundant, more environmentally friendly, and more cost-effective. Therefore, compared with existing methods, the present invention has the advantages of simple operation, easy availability of raw materials, high efficiency, economy, and environmental protection. DETAILED DESCRIPTION

[0019] Example 1

[0020] Add 0.3mmol benzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under sunlight, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0021] The structural characterization data of the obtained product are as follows:

[0022] 1 H NMR(600MHz,Chloroform-d)δ8.05–8.02(m,2H),7.82(d,J=15.7Hz,1H),7.65( dd,J=6.4,3.2Hz,2H),7.61–7.57(m,1H),7.56–7.50(m,3H),7.45–7.40(m,3H).

[0023] 13 C NMR (151MHz, Chloroform-d) δ190.5,144.8,138.1,134.8,132.8,130.5,128.9,128.6,128.5,128.4,122.1.

[0024] According to the above data, the structure of the obtained product is as follows:

[0025]

[0026] Example 2

[0027] Add 0.3mmol benzoyl chloride, 0.2mmol 4-methylstyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0028] The structural characterization data of the obtained product are as follows:

[0029] 1 H NMR(600MHz,Chloroform-d)δ8.04–8.00(m,2H),7.80(d,J=15.7Hz,1H),7.56( dd,J=16.0,7.8Hz,3H),7.53–7.47(m,3H),7.23(d,J=7.8Hz,2H),2.40(s,3H).

[0030] 13 C NMR (151MHz, Chloroform-d) δ190.7,144.9,141.1,138.3,132.6,132.1,129.7,128.6,128.5,128.5,121.1,21.5.

[0031] According to the above data, the structure of the obtained product is as follows:

[0032]

[0033] Example 3

[0034] Add 0.3mmol benzoyl chloride, 0.2mmol 4-tert-butylstyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0035] The structural characterization data of the obtained product are as follows:

[0036] 1H NMR(600MHz,Chloroform-d)δ8.03(dd,J=8.3,1.3Hz,2H),7.82(d,J=15.7Hz,1H),7 .59(dd,J=12.8,7.9Hz,3H),7.53–7.49(m,3H),7.45(d,J=8.4Hz,2H),1.35(s,9H).

[0037] 13 C NMR (151MHz, Chloroform-d) δ190.7,154.2,144.8,138.3,132.6,132.1,128.6,128.4,128.3,125.9,121.3,34.9,31.1.

[0038] According to the above data, the structure of the obtained product is as follows:

[0039]

[0040] Example 4

[0041] Add 0.3mmol benzoyl chloride, 0.2mmol 4-methoxystyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under sunlight, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0042] The structural characterization data of the obtained product are as follows:

[0043] 1 H NMR(600MHz,Chloroform-d)δ8.01(d,J=7.0Hz,2H),7.79(d,J=15.6Hz,1H),7.61–7.55( m,3H),7.50(t,J=7.7Hz,2H),7.42(d,J=15.7Hz,1H),6.94(d,J=8.8Hz,2H),3.85(s,3H).

[0044] 13 C NMR (151MHz, Chloroform-d) δ190.5,161.6,144.7,138.5,132.5,130.2,128.5,128.4,127.6,119.7,114.4,55.4.

[0045] According to the above data, the structure of the obtained product is as follows:

[0046]

[0047] Example 5

[0048] Add 0.3mmol benzoyl chloride, 0.2mmol 4-vinyl biphenyl, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0049] The structural characterization data of the obtained product are as follows:

[0050] 1 H NMR(600MHz,Chloroform-d)δ8.06(dd,J=8.3,1.4Hz,2H),7.88(d,J=15.7Hz,1H),7.73(d,J=8.3Hz,2H) ,7.68–7.63(m,4H),7.62–7.58(m,2H),7.53(t,J=7.6Hz,2H),7.48(t,J=7.7Hz,2H),7.41–7.38(m,1H).

[0051] 13 C NMR (151MHz, Chloroform-d) δ190.4,144.3,143.3,140.1,138.2,133.8,132.7,128.9,128.9,128.6,128.5,127.9,127.5,127.0,121.8.

[0052] According to the above data, the structure of the obtained product is as follows:

[0053]

[0054] Example 6

[0055] Add 0.3mmol benzoyl chloride, 0.2mmol 4-fluorostyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0056] The structural characterization data of the obtained product are as follows:

[0057] 1 H NMR(600MHz,Chloroform-d)δ8.03–8.00(m,2H),7.77(d,J=15.7Hz,1H),7.65–7.61(m,2H ),7.60–7.57(m,1H),7.50(t,J=7.7Hz,2H),7.46(d,J=15.7Hz,1H),7.10(t,J=8.6Hz,2H).

[0058] 13 C NMR(151MHz,Chloroform-d)δ190.2,164.0(d,J 1 C-F =251.868),143.4,138.1,132.8,131.1,130.3(d,J 3 C-F =8.758),128.6,128.4,121.7(d,J 4 C-F =2.265),116.1(d,J 2 C-F =21.895).

[0059] 19 F NMR(565MHz,Chloroform-d)δ-107.57.

[0060] According to the above data, the structure of the obtained product is as follows:

[0061]

[0062] Example 7

[0063] Add 0.3mmol benzoyl chloride, 0.2mmol 4-chlorostyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under sunlight, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0064] The structural characterization data of the obtained product are as follows:

[0065] 1 H NMR(600MHz,Chloroform-d)δ8.04–7.99(m,2H),7.76(d,J=15.7Hz,1H),7.61–7.55(m,3H),7.53–7.49(m,3H),7.39(d,J=8.5Hz,2H).

[0066] 13 C NMR (151MHz, Chloroform-d) δ190.2,143.3,138.0,136.4,133.4,132.9,129.6,129.2,128.6,128.5,122.4.

[0067] According to the above data, the structure of the obtained product is as follows:

[0068]

[0069] Example 8

[0070] Add 0.3mmol benzoyl chloride, 0.2mmol 4-vinyl-benzoic acid methyl ester, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0071] The structural characterization data of the obtained product are as follows:

[0072] 1H NMR(600MHz,Chloroform-d)δ8.07(d,J=8.3Hz,2H),8.04–8.01(m,2H),7.80(d,J=15. 7Hz,1H),7.69(d,J=8.4Hz,2H),7.62–7.58(m,2H),7.51(t,J=7.7Hz,2H),3.93(s,3H).

[0073] 13 C NMR (151MHz, Chloroform-d) δ190.1,166.4,143.2,139.1,137.8,133.0,131.5,130.1,128.7,128.5,128.2,124.1,52.3.

[0074] According to the above data, the structure of the obtained product is as follows:

[0075]

[0076] Example 9

[0077] Add 0.3 mmol benzoyl chloride, 0.2 mmol 3-bromostyrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0078] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0079] The structural characterization data of the obtained product are as follows:

[0080] 1 H NMR (600MHz, Chloroform-d) δ8.04–8.00(m,2H),7.79(s,1H),7.72(d,J=15.7Hz,1H),7.60(t,J=7.4Hz,1H),7.55–7.50(m,5H),7.29(t,J=7.8Hz,1H).

[0081] 13 C NMR (151MHz, Chloroform-d) δ190.0,142.9,137.9,137.0,133.2,133.0,130.8,130.4,128.7,128.5,127.2,123.2,123.1.

[0082] According to the above data, the structure of the obtained product is as follows:

[0083]

[0084] Example 10

[0085] Add 0.3mmol benzoyl chloride, 0.2mmol m-trifluoromethylstyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran to the reaction tube. After 6 hours of reaction at room temperature under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0086] The structural characterization data of the obtained product are as follows:

[0087] 1 H NMR (600MHz, Chloroform-d) δ8.04 (dd, J=8.3, 1.3Hz, 2H), 7.90–7.79 (m, 3H), 7.66 (d, J=8.9Hz, 1H), 7.62–7.51 (m, 5H).

[0088] 13 C NMR(151MHz,Chloroform-d)δ190.0,142.8,137.8,135.7,133.1,131.6,131.5(q,J 2 C-F =32.314),128.7,128.5,126.8(q,J 4 C-F =3.926),124.5(q,J 3 C-F =4.530),123.8(q,J 1 C-F =272.706),123.6.

[0089] 19 F NMR(565MHz,Chloroform-d)δ-62.83.

[0090] According to the above data, the structure of the obtained product is as follows:

[0091]

[0092] Embodiment 11

[0093] Add 0.3mmol benzoyl chloride, 0.2mmol 3-methylstyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0094] The structural characterization data of the obtained product are as follows:

[0095] 1 H NMR(600MHz,Chloroform-d)δ8.03(d,J=8.3Hz,2H),7.80(d,J=15.7Hz,1H),7.59(t,J=7.4Hz,1H), 7.55–7.50(m,3H),7.46(d,J=7.8Hz,2H),7.32(t,J=7.9Hz,1H),7.24(d,J=7.6Hz,1H),2.40(s,3H).

[0096] 13 C NMR (151MHz, Chloroform-d) δ190.6,145.0,138.6,138.2,134.8,132.7,131.4,129.0,128.8,128.6,128.5,125.7,121.8,21.3.

[0097] According to the above data, the structure of the obtained product is as follows:

[0098]

[0099] Example 12

[0100] Add 0.3mmol benzoyl chloride, 0.2mmol 2-methylstyrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0101] The structural characterization data of the obtained product are as follows:

[0102] 1 H NMR(600MHz,Chloroform-d)δ8.13(d,J=15.5Hz,1H),8.04(dd,J=8.3,1.4Hz,2H),7.71(d,J=7.8Hz,1H),7.61–7.57 (m,1H),7.52(t,J=7.7Hz,2H),7.47(d,J=15.5Hz,1H),7.32(td,J=7.4,1.4Hz,1H),7.28–7.23(m,2H),2.49(s,3H).

[0103] 13 C NMR (151MHz, Chloroform-d) δ190.4,142.4,138.3,138.2,133.9,132.8,130.9,130.2,128.6,128.5,126.4,126.3,123.1,19.8.

[0104] According to the above data, the structure of the obtained product is as follows:

[0105]

[0106] Example 13

[0107] Add 0.3mmol benzoyl chloride, 0.2mmol 2-vinylthiophene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0108] The structural characterization data of the obtained product are as follows:

[0109] 1 H NMR(600MHz,Chloroform-d)δ8.01(dd,J=8.3,1.4Hz,2H),7.95(d,J=15.3Hz,1H),7.60–7.56(m,1H),7.50(t,J =7.7Hz,2H),7.42(d,J=5.0Hz,1H),7.36(d,J=3.6Hz,1H),7.34(d,J=15.3Hz,1H),7.09(dd,J=5.1,3.6Hz,1H).

[0110] 13 C NMR (151MHz, Chloroform-d) δ189.9,140.4,138.1,137.3,132.8,132.1,128.8,128.7,128.4,128.4,120.8.

[0111] According to the above data, the structure of the obtained product is as follows:

[0112]

[0113] Embodiment 14

[0114] Add 0.3mmol benzoyl chloride, 0.2mmol 2-phenyl-1-propylene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0115] The structural characterization data of the obtained product are as follows:

[0116] 1 H NMR(600MHz,Chloroform-d)δ8.03–7.98(m,2H),7.59–7.54(m,3H),7.48(t,J=7.6Hz,2H),7.45–7.39(m,3H),7.18(d,J=1.4Hz,1H),2.61(d,J=1.3Hz,3H).

[0117] 13 C NMR (151MHz, Chloroform-d) δ191.9,155.1,142.8,139.3,132.5,129.1,128.6,128.5,128.3,126.5,122.1,18.9.

[0118] According to the above data, the structure of the obtained product is as follows:

[0119]

[0120] Embodiment 15

[0121] Add 0.3mmol benzoyl chloride, 0.2mmol 1,1-diphenylethylene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0122] The structural characterization data of the obtained product are as follows:

[0123] 1 H NMR(600MHz,Chloroform-d)δ7.93(d,J=8.3Hz,2H),7.51–7.48(m,1H),7.40(dt,J=12. 5,5.6Hz,7H),7.29(d,J=6.7Hz,3H),7.21(dt,J=7.8,1.9Hz,2H),7.14(d,J=1.5Hz,1H).

[0124] 13 C NMR (151MHz, Chloroform-d) δ192.7,154.7,141.3,139.0,138.2,132.6,129.7,129.3,128.7,128.5,128.4,128.3,128.0,124.0.

[0125] According to the above data, the structure of the obtained product is as follows:

[0126]

[0127] Example 16

[0128] Add 0.3 mmol benzoyl chloride, 0.2 mmol dihydroprogesterone, 5.0 mol% CuI, 5.0 mol% 1,1'

[0129] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0130] The structural characterization data of the obtained product are as follows:

[0131] 1H NMR(600MHz,Chloroform-d)δ7.78–7.73(m,2H),7.58–7.55(m,1H),7.48(t,J=7.7Hz,2H),7.28(td,J= 7.4,1.4Hz,1H),7.24–7.19(m,2H),7.14(d,J=7.5Hz,2H),2.96(t,J=8.2Hz,2H),2.78(t,J=8.6Hz,2H).

[0132] 13 C NMR (151MHz, Chloroform-d) δ197.4,140.3,138.3,137.4,137.3,132.5,131.6,129.9,129.1,128.8,128.2,127.8,126.7,27.5,22.7.

[0133] According to the above data, the structure of the obtained product is as follows:

[0134]

[0135] Embodiment 17

[0136] Add 0.3mmol benzoyl chloride, 0.2mmol vinyltrimethylsilane, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0137] The structural characterization data of the obtained product are as follows:

[0138] 1 H NMR (600MHz, Chloroform-d) δ7.94(dd,J=8.3,1.4Hz,2H),7.58–7.55(m,1H),7.48(t,J=7.7Hz,2H),7.33–7.23(m,2H),0.20(s,9H).

[0139] 13 C NMR (151MHz, Chloroform-d) δ190.6,149.7,138.0,137.5,132.7,128.8,128.5,-1.8.

[0140] According to the above data, the structure of the obtained product is as follows:

[0141]

[0142] Embodiment 18

[0143] Add 0.3mmol benzoyl chloride, 0.2mmol dimethylphenylvinylsilane, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0144] The structural characterization data of the obtained product are as follows:

[0145] 1 H NMR(600MHz,Chloroform-d)δ7.93(dd,J=8.3,1.4Hz,2H),7.58–7.55(m,3H),7.48(t,J=7.7Hz,2H),7.46–7.36(m,5H),7.31(d,J=18.7Hz,1H),0.50(s,6H).

[0146] 13 C NMR (151MHz, Chloroform-d) δ190.3,147.4,139.4,137.4,136.5,133.9,132.8,129.5,128.8,128.5,128.0,-3.0.

[0147] According to the above data, the structure of the obtained product is as follows:

[0148]

[0149] Embodiment 19

[0150] Add 0.3mmol benzoyl chloride, 0.2mmol L-Phenylalanine, N-[(1,1-dimethylethoxy)carbonyl]-4-ethenyl-,methyl ester, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0151] The structural characterization data of the obtained product are as follows:

[0152] 1 H NMR(600MHz,Chloroform-d)δ8.01(d,J=7.9Hz,2H),7.78(d,J=15.7Hz,1H),7.57(d,J=8.0Hz,3H),7.52–7.48(m,3H),7.19( d,J=7.9Hz,2H),5.05(d,J=6.2Hz,1H),4.61(q,J=6.8Hz,1H),3.72(s,3H),3.12(ddd,J=61.0,13.8,6.1Hz,2H),1.41(s,9H).

[0153] 13 C NMR(151MHz,Chloroform-d)δ190.5,172.1,155.0,144.4,138.9,138.2,133 .6,132.7,130.0,129.9,128.6,128.4,121.8,80.0,54.2,52.3,38.3,28.2.

[0154] HRMS(ESI)m / z:[M+Na] + calcd for(C 24 H 27 NO5Na) + ,432.1781;found:432.1760.

[0155] According to the above data, the structure of the obtained product is as follows:

[0156]

[0157] Embodiment 20

[0158] Add 0.3mmol p-toluyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0159] The structural characterization data of the obtained product are as follows:

[0160] 1 H NMR(600MHz,Chloroform-d)δ7.95(d,J=8.2Hz,2H),7.81(d,J=15.7Hz,1H),7.65(dd,J=7.3,2.2 Hz,2H),7.55(d,J=15.7Hz,1H),7.42(dd,J=5.0,2.3Hz,3H),7.31(d,J=7.6Hz,2H),2.44(s,3H).

[0161] 13 C NMR (151MHz, Chloroform-d) δ189.9,144.3,143.6,135.6,134.9,130.4,129.3,128.9,128.6,128.3,122.0,21.6.

[0162] According to the above data, the structure of the obtained product is as follows:

[0163]

[0164] Embodiment 21

[0165] Add 0.3mmol of p-tert-butylbenzoyl chloride, 0.2mmol of styrene, 5.0mol% of CuI, 5.0mol% of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol of lithium carbonate, and 1.0mL of tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under sunlight, add 0.6mmol of DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0166] The structural characterization data of the obtained product are as follows:

[0167] 1H NMR (600MHz, Chloroform-d) δ7.99(d,J=8.5Hz,2H),7.82(d,J=15.7Hz,1H),7.68–7.64(m,2H),7.58–7.51(m,3H),7.44–7.41(m,3H),1.37(s,9H).

[0168] 13 C NMR (151MHz, Chloroform-d) δ190.0,156.5,144.3,135.5,135.0,130.4,128.9,128.5,128.4,125.6,122.1,35.1,31.1.

[0169] According to the above data, the structure of the obtained product is as follows:

[0170]

[0171] Embodiment 22

[0172] Add 0.3mmol p-methoxybenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0173] The structural characterization data of the obtained product are as follows:

[0174] 1 H NMR(600MHz,Chloroform-d)δ8.05(d,J=8.9Hz,2H),7.81(d,J=15.7Hz,1H),7.64(dd,J=7.4 ,2.1Hz,2H),7.55(d,J=15.6Hz,1H),7.43–7.38(m,3H),6.98(d,J=8.9Hz,2H),3.89(s,3H).

[0175] 13 C NMR (151MHz, Chloroform-d) δ188.7,163.4,143.9,135.0,131.0,130.8,130.3,128.9,128.3,121.8,113.8,55.4.

[0176] According to the above data, the structure of the obtained product is as follows:

[0177]

[0178] Embodiment 23

[0179] Add 0.3mmol 4-fluorobenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0180] The structural characterization data of the obtained product are as follows:

[0181] 1 H NMR(600MHz,Chloroform-d)δ8.08–8.03(m,2H),7.82(d,J=15.7Hz,1H),7.64(dd,J =6.7,2.8Hz,2H),7.51(d,J=15.7Hz,1H),7.46–7.38(m,3H),7.18(t,J=8.6Hz,2H).

[0182] 13 C NMR(151MHz,Chloroform-d)δ188.8,165.6(J 1 C-F =254.586),145.0,134.7,134.5(J 4 C-F =2.869),131.1(J 4 C-F =9.211),130.6,128.9,128.4,121.6,115.0(J 2 C-F =21.744).

[0183] 19 F NMR(565MHz,Chloroform-d)δ-105.54.

[0184] According to the above data, the structure of the obtained product is as follows:

[0185]

[0186] Embodiment 24

[0187] Add 0.3mmol p-chlorobenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0188] The structural characterization data of the obtained product are as follows:

[0189] 1 H NMR (600MHz, Chloroform-d) δ7.97(d,J=8.5Hz,2H),7.82(d,J=15.6Hz,1H),7.64(dd,J=6.4,3.2Hz,2H),7.52–7.45(m,3H),7.44–7.40(m,3H).

[0190] 13 C NMR (151MHz, Chloroform-d) δ189.1,145.3,139.2,136.5,134.7,130.7,129.9,129.0,128.9,128.5,121.5.

[0191] According to the above data, the structure of the obtained product is as follows:

[0192]

[0193] Embodiment 25

[0194] Add 0.3 mmol 4-bromobenzoyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0195] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0196] The structural characterization data of the obtained product are as follows:

[0197] 1H NMR (600MHz, Chloroform-d) δ7.89(d,J=8.5Hz,2H),7.82(d,J=15.7Hz,1H),7.65(d,J=8.5Hz,4H),7.48(d,J=15.7Hz,1H),7.45–7.41(m,3H).

[0198] 13 C NMR (151MHz, Chloroform-d) δ189.4,145.4,136.9,134.7,131.9,130.7,130.0,129.0,128.5,127.9,121.4.

[0199] According to the above data, the structure of the obtained product is as follows:

[0200]

[0201] Embodiment 26

[0202] Add 0.3 mmol 4-iodobenzoyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0203] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran and dichloroethane mixed solvent. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was 20:1 petroleum ether:

[0204] Ethyl acetate mixed solvent.

[0205] The structural characterization data of the obtained product are as follows:

[0206] 1 H NMR(600MHz,Chloroform-d)δ7.87(d,J=8.4Hz,2H),7.81(d,J=15.7Hz,1H),7. 74–7.72(m,2H),7.65–7.63(m,2H),7.46(d,J=15.7Hz,1H),7.44–7.41(m,3H).

[0207] 13 C NMR (151MHz, Chloroform-d) δ189.7,145.5,138.0,137.5,134.7,130.8,129.9,129.0,128.6,121.5,100.6.

[0208] According to the above data, the structure of the obtained product is as follows:

[0209]

[0210] Embodiment 27

[0211] 0.3 mmol of methyl 4-chloroformylbenzoate, 0.2 mmol of styrene, 5.0 mol% of CuI, 5.0 mol% of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2 mmol of lithium carbonate, and 1.0 mL of a mixed solvent of dichloroethane were added to a reaction tube.

[0212] After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol of DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the product was separated and purified by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0213] The structural characterization data of the obtained product are as follows:

[0214] 1 H NMR(600MHz,Chloroform-d)δ8.16(d,J=8.4Hz,2H),8.05(d,J=8.4Hz,2H),7.82(d,J=15.7H z,1H),7.65(dd,J=6.8,2.8Hz,2H),7.51(d,J=15.7Hz,1H),7.45–7.41(m,3H),3.96(s,3H).

[0215] 13 C NMR (151MHz, Chloroform-d) δ190.1,166.3,145.8,141.6,134.6,133.5,130.8,129.8,129.0,128.6,128.3,121.8,52.4.

[0216] According to the above data, the structure of the obtained product is as follows:

[0217]

[0218] Embodiment 28

[0219] Add 0.3mmol o-acetylsalicylic acid chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0220] The structural characterization data of the obtained product are as follows:

[0221] 1 H NMR(600MHz,Chloroform-d)δ7.70(dd,J=7.7,1.7Hz,1H),7.60–7.53(m,4H),7.41 (hept,J=3.8Hz,3H),7.36(td,J=7.6,1.2Hz,1H),7.21–7.15(m,2H),2.24(s,3H).

[0222] 13 C NMR (151MHz, Chloroform-d) δ191.6,169.4,148.7,145.5,134.5,132.5,132.2,130.7,129.8,129.0,128.4,126.0,125.3,123.5,21.0.

[0223] According to the above data, the structure of the obtained product is as follows:

[0224]

[0225] Embodiment 29

[0226] Add 0.3mmol o-methylbenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0227] The structural characterization data of the obtained product are as follows:

[0228] 1H NMR(600MHz,Chloroform-d)δ7.57(dd,J=6.8,2.9Hz,2H),7.50(d,J=8.0Hz,1H),7.48(d,J= 16.1Hz,1H),7.42–7.37(m,4H),7.29(d,J=7.5Hz,2H),7.15(d,J=16.1Hz,1H),2.46(s,3H).

[0229] 13 C NMR (151MHz, Chloroform-d) δ196.5,145.9,139.0,136.9,134.6,131.3,130.6,130.4,128.9,128.4,128.0,126.7,125.4,20.2.

[0230] According to the above data, the structure of the obtained product is as follows:

[0231]

[0232] Embodiment 30

[0233] Add 0.3mmol o-chlorobenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0234] The structural characterization data of the obtained product are as follows:

[0235] 1 H NMR(600MHz,Chloroform-d)δ7.56(dd,J=7.4,2.3Hz,2H),7.50–7.45(m,3H),7.44–7.39(m,4H),7.36(td,J=7.4,1.3Hz,1H),7.14(d,J=16.1Hz,1H).

[0236] 13 C NMR (151MHz, Chloroform-d) δ193.8,146.3,139.0,134.4,131.4,131.2,130.8,130.2,129.3,128.9,128.5,126.8,126.2.

[0237] According to the above data, the structure of the obtained product is as follows:

[0238]

[0239] Embodiment 31

[0240] Add 0.3mmol 2-trifluoromethylbenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0241] The structural characterization data of the obtained product are as follows:

[0242] 1 H NMR(600MHz,Chloroform-d)δ7.77(d,J=9.2Hz,1H),7.65(t,J=6.9Hz,1H),7.60(t,J=7.8Hz,1H),7.53(dd, J=7.7,1.9Hz,2H),7.47(d,J=6.9Hz,1H),7.43–7.37(m,3H),7.30(d,J=16.2Hz,1H),7.05(d,J=16.3Hz,1H).

[0243] 13 C NMR(151MHz,Chloroform-d)δ195.1,147.8,138.8,134.1,131.6,131.0,129.8,129.0,128.5,128.1,127.8(q,J 2 C-F =32.3Hz),126.8,126.7(q,J 3 C-F =4.8Hz),123.6(q,J 1 C-F =273.9Hz).

[0244] According to the above data, the structure of the obtained product is as follows:

[0245]

[0246] Embodiment 32

[0247] Add 0.3 mmol 3-bromobenzoyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0248] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After reacting at room temperature for 6 hours under sunlight, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0249] The structural characterization data of the obtained product are as follows:

[0250] 1 H NMR(600MHz,Chloroform-d)δ8.14(t,J=1.8Hz,1H),7.95–7.93(m,1H),7.83(d,J=15.7Hz,1H), 7.71(ddd,J=7.9,2.0,1.1Hz,1H),7.66–7.64(m,2H),7.48–7.43(m,4H),7.39(t,J=7.8Hz,1H).

[0251] 13 C NMR (151MHz, Chloroform-d) δ189.0,145.7,140.0,135.6,134.6,131.5,130.8,130.2,129.0,128.6,127.0,122.9,121.4.

[0252] According to the above data, the structure of the obtained product is as follows:

[0253]

[0254] Embodiment 33

[0255] Add 0.3mmol 3-(trifluoromethoxy)benzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0256] The structural characterization data of the obtained product are as follows:

[0257] 1 H NMR(600MHz,Chloroform-d)δ7.95(dt,J=7.7,1.3Hz,1H),7.84(d,J=15.8Hz,2H),7.66(d d,J=6.6,3.1Hz,2H),7.55(t,J=8.0Hz,1H),7.48(d,J=15.7Hz,1H),7.44(q,J=3.6Hz,4H).

[0258] 13 C NMR (151MHz, Chloroform-d) δ188.9,149.5,145.9,140.0,134.5,130.9,130.1,129.0,128.6,126.7,125.0,121.3,120.9,120.2(q,J C-F =258.2).

[0259] According to the above data, the structure of the obtained product is as follows:

[0260]

[0261] Embodiment 34

[0262] Add 0.3mmol m-toluoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0263] The structural characterization data of the obtained product are as follows:

[0264] 1 H NMR (600MHz, Chloroform-d) δ7.85–7.79(m,3H),7.65(dd,J=6.5,3.1Hz,2H),7.54(d,J=15.7Hz,1H),7.44–7.38(m,5H),2.45(s,3H).

[0265] 13C NMR (151MHz, Chloroform-d) δ190.7,144.6,138.4,138.2,134.9,133.5,130.4,129.0,128.9,128.4,128.4,125.7,122.2,21.4.

[0266] According to the above data, the structure of the obtained product is as follows:

[0267]

[0268] Embodiment 35

[0269] Add 0.3mmol 3,5-dimethylbenzoyl chloride, 0.2mmol styrene, 5.0mol% CuI, 5.0mol% 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.2mmol lithium carbonate, and 1.0mL tetrahydrofuran to the reaction tube. After reacting at room temperature for 6 hours under 450nm blue light irradiation, add 0.6mmol DBU and stir at room temperature for 30min. Remove the solvent under reduced pressure, separate and purify by column chromatography to obtain the target product. The volume ratio of the column chromatography eluent used is a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0270] The structural characterization data of the obtained product are as follows:

[0271] 1 H NMR(600MHz,Chloroform-d)δ7.81(d,J=15.7Hz,1H),7.68–7.63(m,4H),7.53(d,J=15.7Hz,1H),7.45–7.40(m,3H),7.22(s,1H),2.41(s,6H).

[0272] 13 C NMR (151MHz, Chloroform-d) δ190.8,144.4,138.3,138.2,134.9,134.4,130.4,128.9,128.4,126.2,122.3,21.2.

[0273] According to the above data, the structure of the obtained product is as follows:

[0274]

[0275] Embodiment 36

[0276] Add 0.3 mmol 1-naphthoyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0277] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0278] The structural characterization data of the obtained product are as follows:

[0279] 1 H NMR(600MHz,Chloroform-d)δ8.36(d,J=8.5Hz,1H),8.01(d,J=8.2Hz,1H),7.94–7.91(m,1H), 7.63(d,J=16.1Hz,1H),7.59–7.53(m,5H),7.41(dd,J=5.1,2.0Hz,3H),7.33(d,J=16.0Hz,1H).

[0280] 13 C NMR(151MHz,Chloroform-d)δ195.7,145.9,137.0,134.6,133.8,131.6,130.7,130.5,128.9,128.5,128.4,127.4,127.1,127.1,126.4,125.6,124.5.

[0281] According to the above data, the structure of the obtained product is as follows:

[0282]

[0283] Embodiment 37

[0284] Add 0.3 mmol 2-thiophenecarbonyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0285] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0286] The structural characterization data of the obtained product are as follows:

[0287] 1H NMR (600MHz, Chloroform-d) δ7.89–7.84(m,2H),7.68(dd,J=4.9,1.1Hz,1H),7.64(dd,J=6.4,3.2Hz,2H),7.45–7.41(m,4H),7.19(dd,J=4.9,3.8Hz,1H).

[0288] 13 C NMR (151MHz, Chloroform-d) δ182.0,145.5,144.0,134.6,133.9,131.8,130.6,128.9,128.4,128.2,121.6.

[0289] According to the above data, the structure of the obtained product is as follows:

[0290]

[0291] Embodiment 38

[0292] Add 0.3 mmol furanoyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0293] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0294] The structural characterization data of the obtained product are as follows:

[0295] 1 H NMR (600MHz, Chloroform-d) δ7.88 (d, J=15.8Hz, 1H), 7.64 (dd, J=6.6, 2.2Hz, 3H), 7.45 (d, J= 15.8Hz, 1H), 7.41 (dd, J=5.0, 1.9Hz, 3H), 7.33 (d, J=2.8Hz, 1H), 6.59 (dd, J=3.6, 1.7Hz, 1H).

[0296] 13 C NMR (151MHz, Chloroform-d) δ178.0,153.6,146.5,143.9,134.7,130.6,128.9,128.5,121.1,117.5,112.5.

[0297] According to the above data, the structure of the obtained product is as follows:

[0298]

[0299] Embodiment 39

[0300] Add 0.3 mmol 2-chloronicotinoyl chloride, 0.2 mmol styrene, 5.0 mol% CuI, 5.0 mol% 1,1'

[0301] -binaphthyl-2,2'-bisdiphenylphosphine, 0.2mmol lithium carbonate, 1.0mL tetrahydrofuran. After 6 hours of reaction at room temperature under 450nm blue light irradiation, 0.6mmol DBU was added and stirred at room temperature for 30min. The solvent was removed under reduced pressure, and the target product was obtained by column chromatography separation and purification. The volume ratio of the column chromatography eluent used was a mixed solvent of petroleum ether: ethyl acetate of 20:1.

[0302] The structural characterization data of the obtained product are as follows:

[0303] 1 H NMR(600MHz,Chloroform-d)δ8.52(dd,J=4.8,2.0Hz,1H),7.83(dd,J=7.5,2.0Hz,1H),7.57(dd,J=7.7,1.9 Hz,2H),7.50(d,J=16.1Hz,1H),7.41(d,J=7.8Hz,3H),7.37(dd,J=7.5,4.8Hz,1H),7.16(d,J=16.0Hz,1H).

[0304] 13 C NMR (151MHz, Chloroform-d) δ191.9,151.0,147.8,146.9,138.4,135.4,134.1,131.2,129.1,128.7,125.5,122.5.

[0305] According to the above data, the structure of the obtained product is as follows:

[0306]

Claims

1. A novel method for synthesizing α,β-unsaturated ketones, characterized in that: Using aromatic acid chlorides and olefin derivatives as raw materials, the free radical addition reaction of aromatic acid chlorides with olefins and their derivatives is carried out under photoinduced copper catalysis to obtain α,β-unsaturated ketone compounds.

2. The method for synthesizing the novel α,β-unsaturated ketone according to claim 1, characterized in that This method conforms to the following reaction equation: The aryl acid chloride is Olefin derivatives are Among them, R 1 represents an alkyl group, an alkoxy group, a phenyl group, a halogen group, etc. containing one or more substitutions; R 2 represents a hydrogen atom or an alkyl group containing one or more substitutions; R 3 represents a hydrogen atom or an alkyl group or a phenyl group containing one or more substitutions; R 4 It means an alkyl group, an alkoxy group, a phenyl group, a halogen group, etc. containing one or more substitutions.

3. The method for synthesizing an α,β-unsaturated ketone according to claim 1, characterized in that: The copper catalyst is one or a mixture of two or more of CuCl, CuBr, CuI, Cu2O, and Cu2O.

4. The method for synthesizing an α,β-unsaturated ketone according to claim 1, characterized in that The operation was carried out according to the following steps: an olefin derivative, aromatic acid chloride, copper catalyst, ligand, base and solvent were added to a reaction tube, and the reaction was stirred for 6 hours under N2 protection and light irradiation. After the reaction, DBU was added and the reaction was stirred for 30 minutes in air and room temperature. The crude product was filtered and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain an α,β-unsaturated ketone compound.

5. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The light is 450nm wavelength blue light or sunlight.

6. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The molar ratio of the aryl acid chloride to the olefin derivative is 3:

2.

7. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The ligand is 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP).

8. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The base is one or a mixture of two or more of lithium carbonate, potassium dihydrogen phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, and 2,6-di-tert-butyl-4-methylpyridine.

9. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The solvent is one or a mixture of two or more of tetrahydrofuran, fluorobenzene, trifluorotoluene, 1,4-dioxane, N,N-dimethylacetamide, cyclopentyl methyl ether, 2-methyltetrahydrofuran, dichloroethane and acetonitrile.

10. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The reaction tube is a quartz tube or a glass tube.

11. The method for synthesizing an α,β-unsaturated ketone according to claim 4, characterized in that: The eluent in the column chromatography is petroleum ether or a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of (20-100):1.

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