Preparation method of N-butenyl amide compound

Abstract

The invention discloses a preparation method of an N-butenyl amide compound, and belongs to the technical field of chemical synthesis, N-aryloxy amide and benzenesulfonyl substituted olefin are used as raw materials, and the N-butenyl amide compound is obtained through free radical amidation reaction of olefin under the action of a photocatalyst. The invention provides a novel synthesis method for preparation of the N-butenyl amide compound, and the obtained product has an amide structural unit and an alkenyl unit at the same time, can be used as an amidation reagent, can also be used as a class of alkenyl synthesis units, and can be used for preparing the N-butenyl amide compound. The method provides new choices and paths for synthesis, modification and modification of various natural products, drug molecules and bioactive molecules containing amide structural units, and is expected to be widely applied to the fields of organic synthesis, drug development, high polymer materials and the like.

Description

Technical Field

[0001] The present invention belongs to the technical fields of chemical synthesis, medicinal chemistry and material chemistry, and particularly relates to a N - Preparation method of butenyl amide compounds. Background Art

[0002] Amide building blocks are important components of bioactive molecules, including peptides, proteins, chemical probes, and various clinically approved and naturally derived drugs. In recent years, the amine alkylation reaction of olefins is one of the effective ways to construct amine compounds, among which photocatalytic redox is a hot research field with unique advantages. However, there are few reports on the construction of amide compounds through the free radical amidation strategy of olefins, so it is still worth exploring the development of a free radical olefin amidation reaction method to construct complex amides.

[0003] In recent years, free radical strategies have been used to achieve amine alkylation of olefins, usually using tertiary amine compounds as free radical precursors to generate nitrogen α-carbon center free radicals, which then add to olefins to obtain amine alkylation products of olefins. However, due to the difficulty in generating amide nitrogen α-carbon center free radicals, the free radical amidation reaction of olefins has not been sufficiently developed and studied. The present invention develops a new method for generating amide nitrogen α-carbon center free radicals and uses it for N -Efficient synthesis of butenyl amide compounds, which have widely applicable amide structural units and olefin synthons that can undergo various transformations, showing high research value. Summary of the invention

[0004] The object of the present invention is to provide a N -Butenylamide compound preparation method, in order to solve the above-mentioned existing problems in the prior art. So far, there is no report on the reaction of synthesizing long-chain terminal olefin amide based on amide nitrogen α carbon center free radical strategy. N -Butenyl amide compounds have wider compatibility and application range, many of which are difficult to synthesize using existing methods.

[0005] A sort of N - a method for preparing a butenyl amide compound, comprising: N -aryloxyamide and benzenesulfonyl substituted olefin are added to an alkaline organic solvent, a free radical initiator is added, and the free radical amidation reaction of the olefin is performed under light to prepare the N -Butenyl amide compounds.

[0006] The present invention N-Aryloxyamide is the free radical source of amide nitrogen α carbon center, benzenesulfonyl substituted olefin is the free radical acceptor, photosensitizer, base and organic solvent are added to the system in sequence, and the reaction is carried out under light conditions. The generated amide nitrogen α carbon center free radical adds to the olefin and then removes the benzenesulfonyl group, finally obtaining N -Butenyl amide products.

[0007] Preferably, the general formula of the free radical amidation reaction of olefin is:

[0008] Among them, R 1 , R 2 , R 3 is independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, an ester group, an aryl group, a substituted aryl group, an aromatic heterocycle or an aromatic heterocycle derivative group, and Ar is 4-nitrophenyl.

[0009] Preferably, the free radical initiator is Pd(PPh 3 ) 2 Cl 2 、Ni(PPh 3 ) 2 Cl 2 、CuCl、Cu(TC)、Cu(MeCN) 4 PF 6 、FeCl 3 , Eosin Y, 4CzIPN, TPT, Rhodamine B, fac -Ir(ppy) 3 、Ir(ppy) 2 PF 6 、Ir[ppy] 2 (dtbbpy)PF 6 、Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 、Mes-Acr-Me-ClO 4 、Mes-( t -Bu) 2 Acr-Ph-BF 4 、Mes-Acr-I、Mes-Acr-Me-PF 6 , Mes-Acr-Ph-Cl, Mes-Acr-Ph-BF 4 、Ru(bpz) 3 (PF 6 ) 2 、Ru(bpy) 3 Cl 2 、Ru(PPh3 ) 2 Cl 2 、Ru(PPh 3 ) 3 Cl 2 One or more of .

[0010] Preferably, the organic solvent is dichloroethane, acetonitrile, tetrahydrofuran, N , N -Dimethylformamide (DMF), N , N - one or more of dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), 1,4-dioxane, isopropanol.

[0011] Preferably, the present invention is carried out by adding NaHCO to the organic solvent 3 、Na 2 CO 3 , K 2 CO 3 , K 3 PO 4 , LiOH, triethylamine (Et 3 N) and isopropylethylamine (DIPEA) to prepare the basic organic solvent.

[0012] Preferably, the N - The molar ratio of aryloxyamide to benzenesulfonyl olefin is 1.2-3.0:1.

[0013] Preferably, the wavelength of the light is 360~500nm.

[0014] More preferably, the wavelength of the light is 460 nm.

[0015] Preferably, the free radical amidation reaction is carried out at room temperature, and the reaction time is 2-48 hours.

[0016] Compared with the prior art, the present invention has the following advantages and technical effects: 1. The present invention is based on N -aryloxyamide and benzenesulfonyl substituted olefin are used as raw materials, and amide nitrogen free radicals are generated under the action of free radical initiator and light to undergo intramolecular 1,2-hydrogen atom migration (HAT). The obtained amide α carbon center free radical is added to the olefin, and the leaving group is further removed to undergo free radical amidation reaction to prepare the N -Butenyl amide compounds, the amide and olefinic framework in the product structure are part of the molecular structure of various drugs, the present invention is NThe preparation of -butenyl amide compounds provides a new synthetic method. The obtained product has both amide structural units and alkenyl units. It can be used as an amidation reagent and also as a type of alkenyl synthetic unit. It provides new options and paths for the synthesis, modification and modification of various natural products, drug molecules and bioactive molecules containing amide structural units, and is expected to be widely used in organic synthesis, drug development and polymer materials.

[0017] 2. The present invention adopts a free radical reaction, which can be initiated by simple illumination, with mild reaction conditions, high yield, low instrument and equipment requirements, and simple operation; 3. The method of the present invention has good compatibility and is applicable to amides and benzenesulfonyl olefins substituted with various types of groups and multiple sites, and can be used for a variety of N -Synthesis of butenyl amides. DETAILED DESCRIPTION

[0018] The following is a detailed description of the technical solutions in the embodiments of the present invention in combination with preferred embodiments and data. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] It should be noted that all professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be purchased from the market or prepared by existing methods.

[0020] Example 1

[0021] Add Ir(ppy) to the dry Schlenk tube 2 PF 6 (0.004mmol, 2mol%), N -aryloxybenzamide (1a, 0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3a, 32 mg, yield: 65%).

[0022] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3a prepared in Example 1 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.78–7.76 (m, 2H), 7.50–7.48 (m, 1H), 7.44–7.42 (m, 2H), 6.68 (br s, 1H), 6.27 (s, 1H), 5.70 (s, 1H), 4.24 (q, J =7.1 Hz, 2H), 3.62 (q, J = 6.3 Hz, 2H), 2.65 (t, J = 6.5 Hz, 2H), 1.31 (t, J = 7.1Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d 167.5, 167.4, 138.1, 134.5, 131.4,128.5, 127.3, 126.8, 61.1, 39.7, 31.8, 14.1; HRMS (ESI) calculation for C 14 H 18 NO 3 + (M + H) + 248.1281, found 248.1281.

[0023] Example 2

[0024]

[0025] To a dry Schlenk tube were added 4CzIPN (0.004 mmol, 2 mol%), N-aryloxybenzamide (1a, 0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3a, 38 mg, yield: 76%).

[0026] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3a prepared in Example 2 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.78–7.76 (m, 2H), 7.50–7.48 (m, 1H), 7.44–7.42 (m, 2H), 6.68 (br s, 1H), 6.27 (s, 1H), 5.70 (s, 1H), 4.24 (q, J =7.1 Hz, 2H), 3.62 (q, J = 6.3 Hz, 2H), 2.65 (t, J = 6.5 Hz, 2H), 1.31 (t, J = 7.1Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d 167.5, 167.4, 138.1, 134.5, 131.4,128.5, 127.3, 126.8, 61.1, 39.7, 31.8, 14.1; HRMS (ESI) calculation for C 14 H 18 NO 3 + (M + H) + 248.1281, found 248.1281.

[0027] Example 3

[0028]

[0029] Add Mes-Acr-Me-ClO to the dry Schlenk tube. 4 (0.004mmol, 2mol%), N -aryloxybenzamide (1a, 0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3a, 28 mg, yield: 57%).

[0030] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3a prepared in Example 3 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.78–7.76 (m, 2H), 7.50–7.48 (m, 1H), 7.44–7.42 (m, 2H), 6.68 (br s, 1H), 6.27 (s, 1H), 5.70 (s, 1H), 4.24 (q, J =7.1 Hz, 2H), 3.62 (q, J = 6.3 Hz, 2H), 2.65 (t, J = 6.5 Hz, 2H), 1.31 (t, J = 7.1Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d 167.5, 167.4, 138.1, 134.5, 131.4,128.5, 127.3, 126.8, 61.1, 39.7, 31.8, 14.1; HRMS (ESI) calculation for C 14 H 18 NO 3+ (M + H) + 248.1281, found 248.1281.

[0031] Example 4

[0032]

[0033] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), N -aryloxybenzamide (1a, 0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3a, 43 mg, yield: 87%).

[0034] Example 4 The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the prepared product 3a are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.78–7.76 (m, 2H), 7.50–7.48 (m, 1H), 7.44–7.42 (m, 2H), 6.68 (br s, 1H), 6.27 (s, 1H), 5.70 (s, 1H), 4.24 (q, J =7.1 Hz, 2H), 3.62 (q, J = 6.3 Hz, 2H), 2.65 (t, J = 6.5 Hz, 2H), 1.31 (t, J = 7.1Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d167.5, 167.4, 138.1, 134.5, 131.4,128.5, 127.3, 126.8, 61.1, 39.7, 31.8, 14.1; HRMS (ESI) calculation for C 14 H 18 NO 3 + (M + H) + 248.1281, found 248.1281.

[0035] Example 5

[0036]

[0037] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1b (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3b, 37 mg, yield: 71%).

[0038] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3b prepared in Example 5 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.32-7.27 (m, 2H), 7.21-7.16 (m, 2H),6.27 (br s, 1H), 6.26 (d, J = 1.2 Hz, 1H), 6.03 (br s, 1H), 5.69 (d, J = 1.3 Hz,1H), 4.22 (q, J = 7.1 Hz, 2H), 3.61 (q, J= 6.4 Hz, 2H), 2.64 (t, J = 6.6 Hz, 2H),2.43 (s, 3H), 1.31 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 170.1, 167.0, 137.8, 136.4, 136.0,131.0, 129.8, 127.1, 126.6, 125.7, 61.0, 38.9, 32.0, 19.8, 14.1; HRMS (ESI) calculation for C 15 H 20 NO 3 + (M + H) + 262.1438, found 262.1437.

[0039] Example 6

[0040]

[0041] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1c (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3c, 40 mg, yield: 76%).

[0042] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3c prepared in Example 6 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d7.59 (s, 1H), 7.55–7.48 (m, 1H), 7.32-7.28 (m, 2H), 6.59 (br s, 1H), 6.25 (d, J = 1.3 Hz, 1H), 5.68 (d, J = 1.3 Hz,1H), 4.23 (q, J = 7.1 Hz, 2H), 3.60 (q, J = 6.4 Hz, 2H), 2.63 (t, J = 6.6 Hz, 2H),2.38 (s, 3H), 1.30 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.6, 167.4, 138.3, 138.1, 134.5,132.1, 128.4, 127.6, 127.3, 123.7, 61.0, 39.5, 31.8, 21.3, 14.1; HRMS (ESI) calculation for C 15 H 20 NO 3 + (M + H) + 262.1438, found 262.1440.

[0043] Example 7

[0044] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1d (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, and the reaction system was placed under 460nm blue light and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3d, 39 mg, yield: 75%).

[0045] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3d prepared in Example 7 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.68–7.66 (m, 2H), 7.24–7.22 (m, 2H), 6.61 (br s, 1H), 6.26 (d, J = 1.1 Hz, 1H), 5.69 (d, J = 0.8 Hz, 1H), 4.23 (q, J =7.1 Hz, 2H), 3.60 (q, J = 6.4 Hz, 2H), 2.64 (t, J = 6.5 Hz, 2H), 2.39 (s, 3H), 1.31 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.5, 167.3, 141.8, 138.1, 131.6,129.2, 127.3, 126.8, 61.1, 39.6, 31.8, 21.4, 14.1; HRMS (ESI) calculation for C 15 H 19 NO 3 Na + (M + Na) + 284.1257, found 284.1254.

[0046] Example 8

[0047] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2(0.004mmol, 2mol%), 1e (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, and the reaction system was placed under 460nm blue light and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3e, 43 mg, yield: 81%).

[0048] The hydrogen spectrum, carbon spectrum, fluorine spectrum and high-resolution mass spectrum data of the product 3e prepared in Example 8 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.79–7.77 (m, 2H), 7.11–7.08 (m, 2H), 6.70 (br s, 1H), 6.26 (s, 1H), 5.70 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H), 3.59 (q, J = 5.9 Hz, 2H), 2.63 (t, J = 6.5 Hz, 2H), 1.31 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.7, 166.3, 164.7 (d, J = 251.7 Hz),138.2, 130.6 (d, J = 3.5 Hz), 129.1 (d, J = 8.8 Hz), 127.5, 115.5 (d, J = 21.8 Hz),61.2, 40.0, 31.7, 14.1; 19 F NMR (377 MHz, Chloroform- d ) d-113.30; HRMS (ESI) calculation for C 14 H 17 FNO 3 + (M + H) + 266.1187, found 266.1190.

[0049] Example 9

[0050] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1f (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3f, 46 mg, yield: 82%).

[0051] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3f prepared in Example 9 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.71 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.5Hz, 2H), 6.78 (br s, 1H), 6.25 (s, 1H), 5.69 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H),3.58 (q, J = 6.1 Hz, 2H), 2.63 (t, J = 6.4 Hz, 2H), 1.30 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, Chloroform- d ) d 167.7, 166.3, 138.2, 137.6, 132.8,128.7, 128.3, 127.5, 61.2, 40.0, 31.7, 14.1; HRMS (ESI) calculation for C 14 H 17 ClNO 3 + (M + H) + 282.0891, found 282.0890.

[0052] Example 10

[0053] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1g (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3 g, 52 mg, yield: 80%).

[0054] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3g prepared in Example 10 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.64 (d, J = 8.6 Hz, 2H), 7.54 (s, 2H), 6.77 (br s, 1H), 6.25 (d, J = 1.0 Hz, 1H), 5.69 (d, J = 0.92 Hz, 1H), 4.23 (q, J=7.1 Hz, 2H), 3.58 (q, J = 6.2 Hz, 2H), 2.63 (t, J = 6.4 Hz, 2H), 1.31 (t, J = 7.1Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.7, 166.3, 138.2, 133.3, 131.7,128.5, 127.5, 126.0, 61.2, 40.0, 31.7, 14.1; HRMS (ESI) calculation for C 14 H 17 BrNO 3 + (M + H) + 326.0386, found 326.0384.

[0055] Embodiment 11

[0056] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1h (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3h, 47 mg, yield: 77%).

[0057] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3h prepared in Example 11 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.70 (d, J= 8.3 Hz, 2H), 7.43 (d, J = 8.4Hz, 2H), 6.61 (br s, 1H), 6.25 (s, 1H), 5.68 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H),3.60 (q, J = 6.2 Hz, 2H), 2.63 (t, J = 6.5 Hz, 2H), 1.32 (s, 9H), 1.29 (d, J = 7.1Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.5, 167.3, 154.8, 138.1, 131.6,127.2, 126.6, 125.4, 61.0, 39.5, 34.9, 31.8, 31.1, 14.1; HRMS (ESI) calculation for C 18 H 26 NO 3 + (M + H) + 304.1907, found 304.1907.

[0058] Example 12

[0059] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1i (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, and the reaction system was placed under 460nm blue light and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a white solid product (3i, 52 mg, yield: 83%, melting point: 69-70°C).

[0060] The hydrogen spectrum, carbon spectrum, fluorine spectrum and high-resolution mass spectrum data of the product 3i prepared in Example 12 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.90 (d, J = 8.1 Hz, 2H), 7.69 (d, J =8.2 Hz, 2H), 6.97 (br s, 1H), 6.28 (d, J = 0.8 Hz, 1H), 5.73 (s, 1H), 4.24 (q, J = 7.1 Hz, 2H), 3.62 (q, J = 5.8 Hz, 2H), 2.65 (t, J = 6.4 Hz, 2H), 1.32 (t, J = 7.1Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.8, 166.0, 138.1, 137.7, 133.0 (q, J = 33.0 Hz), 127.7, 127.3, 125.6 (q, J = 3.7 Hz), 123.7 (q, J = 272.5 Hz), 70.1,61.2, 40.2, 31.6, 14.1; 19 F NMR (377 MHz, Chloroform-d) d -62.9; HRMS (ESI) calculation for C 15 H 17 F 3 NO 3 + (M + H) + 316.1155, found 316.1154.

[0061] Embodiment 13

[0062] Add Ru(bpy) to the dry Schlenk tube. 3 Cl2 (0.004mmol, 2mol%), 1j (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3j, 46 mg, yield: 80%).

[0063] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3j prepared in Example 13 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.96 (d, J = 8.1 Hz, 2H), 7.84 (d, J = 8.2Hz, 2H), 6.99 (br s, 1H), 6.24 (s, 1H), 5.69 (s, 1H), 4.21 (q, J = 7.1 Hz, 2H),3.59 (q, J = 6.1 Hz, 2H), 2.63 (t, J = 6.7 Hz, 2H), 2.60 (s, 3H), 1.29 (t, J = 7.1Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 197.5, 167.6, 166.3, 139.0, 138.3,138.1, 128.4, 127.4, 127.2, 61.1, 40.0, 31.6, 26.7, 14.1; HRMS (ESI) calculation for C 16 H 20 NO 4 + (M + H) +290.1387, found 290.1387.

[0064] Embodiment 14

[0065] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1k (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3k, 47 mg, yield: 85%).

[0066] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3k prepared in Example 14 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.35 (s, 2H), 7.11 (s, 1H), 6.51 (brs, 1H), 6.28 – 6.23 (m, 1H), 5.68 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H), 3.59 (q, J =6.4 Hz, 2H), 2.63 (t, J = 6.5 Hz, 2H), 2.34 (s, 6H), 1.31 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 168.1, 167.7, 138.5, 138.4, 134.8,133.2, 127.5, 124.9, 61.3, 39.8, 32.1, 21.5, 14.5; HRMS (ESI) calculation for C 16 H 22 NO 3 + (M + H) + 276.1594, found 276.1595.

[0067] Embodiment 15

[0068] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1l (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (31, 51 mg, yield: 75%).

[0069] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 31 prepared in Example 15 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.03 (s, 2H), 6.87 (s, 1H), 6.25 (s,1H), 5.71 (s, 1H), 4.21 (q, J = 7.1 Hz, 2H), 3.89 (s, 6H), 3.86 (s, 3H), 3.57(q, J = 6.1 Hz, 2H), 2.62 (t, J = 6.4 Hz, 2H), 1.30 (t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d167.7, 166.7, 152.9, 140.5, 138.1,129.6, 127.3, 104.0, 60.9, 60.6, 56.0, 40.0, 31.5, 13.9; HRMS (ESI) calculation for C 17 H 24 NO 6 + (M + H) + 338.1598, found 338.1595.

[0070] Example 16

[0071] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1m (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, and the reaction system was placed under 460nm blue light and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3m, 46 mg, yield: 78%).

[0072] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3m prepared in Example 16 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 8.30 (s, 1H), 7.92 (d, J = 7.8 Hz, 1H),7.90–7.86 (m, 2H), 7.83 (dd, J = 8.5, 1.7 Hz, 1H), 7.59–7.51 (m, 2H), 6.81 (brs, 1H), 6.29 (d, J = 1.3 Hz, 1H), 5.72 (d, J= 0.9 Hz, 1H), 4.25 (q, J = 7.1 Hz,2H), 3.68 (q, J = 6.3 Hz, 2H), 2.69 (t, J = 6.5 Hz, 2H), 1.32 (t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d 167.4, 167.2, 138.0, 134.5, 132.4,131.5, 128.7, 128.2, 127.5, 127.3, 127.2, 127.1, 126.5, 123.3, 60.9, 39.6,31.6, 14.0; HRMS (ESI) calculation for C 18 H 20 NO 3 + (M + H) + 298.1438, found 298.1436.

[0073] Embodiment 17

[0074] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1n (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3n, 39 mg, yield: 79%).

[0075] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3n prepared in Example 17 are as follows: 1H NMR (600 MHz, Chloroform- d ) d 8.54 (d, J = 4.6 Hz, 1H), 8.19 (d, J =7.8 Hz, 1H), 8.17 (br s, 1H), 7.87–7.81 (m, 1H), 7.45–7.40 (m, 1H), 6.27 (d, J = 1.2 Hz, 1H), 5.66 (d, J = 1.3 Hz, 1H), 4.23 (q, J = 7.1 Hz, 2H), 3.65 (q, J = 6.7Hz, 2H), 2.66 (t, J = 6.8 Hz, 2H), 1.32 (t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d 167.0, 164.5, 150.1, 148.2, 137.9,137.5, 127.1, 126.3, 122.4, 61.1, 38.5, 32.3, 14.4. HRMS (ESI) calculation for C 13 H 17 N 2 O 3 + (M + H) + 249.1234, found 249.1238.

[0076] Embodiment 18

[0077] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2(0.004mmol, 2mol%), 1o (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3o, 35 mg, yield: 74%).

[0078] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3o prepared in Example 18 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.45 (s, 1H), 7.12 (d, J = 3.3 Hz, 1H), 6.62 (br s, 1H), 6.51 (dd, J = 3.4, 1.7 Hz, 1H), 6.29 (s, 1H), 5.69 (s, 1H), 4.25 (q, J = 7.1 Hz, 2H), 3.61 (q, J = 6.5 Hz, 2H), 2.64 (t, J = 6.7 Hz, 2H), 1.34(t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, Chloroform- d ) d 167.2, 158.5, 148.1, 143.9, 137.9,127.3, 114.1, 112.2, 61.1, 38.5, 32.1, 14.3; HRMS (ESI) calculation for C 12 H 16 NO 4 + (M + H) + 238.1074, found 238.1075.

[0079] Embodiment 19

[0080] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1o (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3p, 40 mg, yield: 80%).

[0081] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3p prepared in Example 19 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.50-7.43 (m, 2H), 7.07 (dd, J = 5.0,3.7 Hz, 1H), 6.61 (br s, 1H), 6.26 (d, J = 1.2 Hz, 1H), 5.70 (d, J = 1.1 Hz, 1H),4.24 (q, J = 7.1 Hz, 2H), 3.58 (q, J = 6.4 Hz, 2H), 2.63 (t, J = 6.4 Hz, 2H), 1.32(t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d167.6, 161.8, 139.1, 138.0, 129.7,127.8, 127.5, 127.5, 61.1, 39.7, 31.8, 14.1; HRMS (ESI) calculation for C 12 H 16 NO 3 S + (M + H) + 254.0846 found 254.0849.

[0082] Embodiment 20

[0083] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1q (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3q, 32 mg, yield: 70%).

[0084] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3q prepared in Example 20 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 6.24 (d, J = 1.1 Hz, 1H), 5.71 (br s,1H), 5.62 (d, J = 1.04 Hz, 1H), 4.23 (q, J = 7.1 Hz, 2H), 3.41 (q, J = 6.5 Hz, 2H),3.03–2.93 (m, 1H), 2.53 (t, J= 6.5 Hz, 2H), 2.31–2.21 (m, 2H), 2.19–2.08 (m,2H), 2.02–1.91 (m, 1H), 1.91–1.84 (m, 1H), 1.33 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 175.0, 167.2, 137.9, 127.0, 61.0,39.9, 38.6, 31.9, 25.3, 18.1, 14.2; HRMS (ESI) calculation for C 12 H 20 NO 3 + (M + H) + 226.1438, found 226.1438.

[0085] Embodiment 21

[0086] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1r (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, and the reaction system was placed under 460nm blue light and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to give a colorless oily product (3r, 35 mg, yield: 69%).

[0087] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3r prepared in Example 21 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d6.22 (s, 1H), 5.75 (br s, 1H), 5.61 (s, 1H), 4.22 (q, J = 7.1 Hz, 2H), 3.39 (q, J = 6.4 Hz, 2H), 2.51 (t, J = 6.6 Hz,2H), 2.03 (tt, J = 11.8, 3.3 Hz, 1H), 1.84–1.75 (m, 4H), 1.39 (q, J = 11.6 Hz,2H), 1.31 (t, J = 7.1 Hz, 3H), 1.24 (q, J = 10.8, 8.6 Hz, 4H); 13 C NMR (101 MHz, Chloroform- d ) d 176.1, 167.2, 137.9, 127.0, 60.9,45.5, 38.5, 31.9, 29.7, 25.7, 14.2; HRMS (ESI) calculation for C 14 H 24 NO 3 + (M + H) + 254.1751, found 254.1751.

[0088] Embodiment 22

[0089] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1s (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3s, 41 mg, yield: 74%).

[0090] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3s prepared in Example 22 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.37 (s, 5H), 6.24 (s, 1H), 5.62 (s,1H), 5.11 (s, 2H), 4.92 (br s, 1H), 4.25–4.13 (m, 2H), 3.39 (q, J = 6.4 Hz,2H), 2.55 (t, J = 6.6 Hz, 2H), 1.32 (t, J = 6.9 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.2, 156.6, 137.9, 136.9, 128.8,128.4, 127.3, 66.9, 61.2, 40.3, 32.7, 14.5; HRMS (ESI) calculation for C 15 H 20 NO 4 + (M + H) + 278.1387, found 278.1387.

[0091] Embodiment 23

[0092] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2(0.004mmol, 2mol%), 1t (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3t, 33 mg, yield: 61%).

[0093] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3t prepared in Example 23 are as follows: 1 H NMR (600 MHz, Chloroform- d ) d 7.61 (d, J = 15.6 Hz, 1H), 7.52–7.48 (m,2H), 7.36 (q, J = 6.2 Hz, 3H), 6.37 (d, J = 15.6 Hz, 1H), 6.26 (d, J = 1.0 Hz, 1H),5.99 (br s, 1H), 5.70–5.67 (m, 1H), 4.24 (q, J = 7.1 Hz, 2H), 3.55 (q, J = 6.5Hz, 2H), 2.60 (t, J = 6.5 Hz, 2H), 1.33 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) d 167.3, 165.9, 140.9, 137.9, 134.8,129.6, 128.8, 127.7, 127.2, 120.6, 61.0, 39.1, 31.9, 14.1; HRMS (ESI) calculation for C 16 H 20 NO3 + (M + H) + 274.1438, found 274.1439.

[0094] Embodiment 24

[0095] Add Ru(bpy) to the dry Schlenk tube. 3 Cl 2 (0.004mmol, 2mol%), 1u (0.4mmol), then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), acetonitrile (2.0mL, 0.1M) were added under nitrogen atmosphere, the reaction system was placed under 460nm blue light, and stirred at room temperature for 24h. After the reaction was completed, water was added to quench, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L), washed once with saturated brine, and then washed with Na 2 SO 4 The residue was dried, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain a colorless oily product (3u, 45 mg, yield: 60%).

[0096] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3u prepared in Example 24 are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.86–7.79 (m, 2H), 7.52–7.46 (m, 1H), 7.45–7.38 (m, 2H), 7.35 (d, J = 8.5 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 7.21 (d, J =7.2 Hz, 1H), 6.27 (s, 1H), 5.72 (s, 1H), 5.28-5.22 (m, 1H), 4.22 (q, J = 7.1Hz, 2H), 3.00–2.79 (m, 2H), 1.32 (s, 9H), 1.28 (d, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, Chloroform-d ) d 168.5, 166.6, 150.3, 139.1, 137.4,134.4, 131.5, 128.6, 128.5, 127.1, 126.1, 125.7, 61.4, 54.7, 38.6, 34.6,31.5, 14.3; HRMS (ESI) calculation for C 24 H 30 NO 3 + (M + H) + 380.2220, found 380.2220. The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A method for preparing N-butenyl amide compounds, characterized in that: N-aryloxyamide and benzenesulfonyl substituted olefin are added into a basic organic solvent, a free radical initiator is added, and the N-butenyl amide compound is prepared through a free radical amidation reaction of the olefin under light.

2. The preparation method according to claim 1, characterized in that: The general formula for the free radical amidation reaction of the olefin is: Among them, R 1 , R 2 , R 3 is independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, an ester group, an aryl group, a substituted aryl group, an aromatic heterocycle or an aromatic heterocycle derivative group, and Ar is 4-nitrophenyl.

3. The preparation method according to claim 1, characterized in that: The free radical initiator is one or more of Pd(PPh3)2Cl2, Ni(PPh3)2Cl2, CuCl, Cu(TC), Cu(MeCN)4PF6, FeCl3, Eosin Y, 4CzIPN, TPT, Rhodamine B, fac-Ir(ppy)3, Ir(ppy)2bpyPF6, Ir[ppy]2(dtbbpy)PF6, Ir[dF(CF3)ppy]2(dtbbpy)PF6, Mes-Acr-Me-ClO4, Mes-(t-Bu)2Acr-Ph-BF4, Mes-Acr-I, Mes-Acr-Me-PF6, Mes-Acr-Ph-Cl, Mes-Acr-Ph-BF4, Ru(bpz)3(PF6)2, Ru(bpy)3Cl2, Ru(PPh3)2Cl2, and Ru(PPh3)3Cl2.

4. The preparation method according to claim 1, characterized in that: The organic solvent is one or more of dichloroethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, and isopropanol.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the N-aryloxyamide to the benzenesulfonyl olefin is 1.2-3.0:

1.

6. The preparation method according to claim 1, characterized in that: The wavelength of the light is 360-500 nm.

7. The preparation method according to claim 6, characterized in that: The wavelength of the light is: 460nm.

8. The preparation method according to claim 1, characterized in that: The free radical amidation reaction is carried out at room temperature, and the reaction time is 2-48 hours.

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