A method for preparing N-butenyl amide compounds

Abstract

The invention discloses a method for preparing N-butenyl amide compounds, which belongs to the technical field of chemical synthesis. N-aryloxyamide and benzenesulfonyl substituted olefin are used as raw materials, and under the action of a photocatalyst, the N-butenyl amide compounds are obtained by free radical amidation reaction of olefin. The invention provides a new synthesis method for the preparation of N-butenyl amide compounds, and the obtained product has both an amide structural unit and an alkenyl unit, which can be used as an amidating agent and a class of alkenyl synthesis units, and provides new options and paths for the synthesis, modification and modification of a variety of natural products, drug molecules and bioactive molecules containing amide structural units, and is expected to be widely used in the fields of organic synthesis, drug development and polymer materials.

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]

[0009] 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.

[0010] Preferably, the free radical initiator is 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, Ru(PPh3)3Cl2 or more.

[0011] 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.

[0012] Preferably, the present invention prepares the alkaline organic solvent by adding one of NaHCO3, Na2CO3, K2CO3, K3PO4, LiOH, triethylamine (Et3N) and isopropylethylamine (DIPEA) to the organic solvent.

[0013] Preferably, the N - The molar ratio of aryloxyamide to benzenesulfonyl olefin is 1.2-3.0:1.

[0014] Preferably, the wavelength of the light is 360~500nm.

[0015] More preferably, the wavelength of the light is 460 nm.

[0016] Preferably, the free radical amidation reaction is carried out at room temperature, and the reaction time is 2-48 hours.

[0017] Compared with the prior art, the present invention has the following advantages and technical effects:

[0018] 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 N The 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.

[0019] 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;

[0020] 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

[0021] 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.

[0022] 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.

[0023] Example 1

[0024]

[0025] Ir(ppy)2bpyPF6 (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, 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, dried over Na2SO4, 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 (3a, 32mg, yield: 65%).

[0026] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3a prepared in Example 1 are as follows:

[0027] 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);

[0028] 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;

[0029] HRMS (ESI) calculation for C 14 H 18 NO3 + (M + H) + 248.1281, found 248.1281.

[0030] Example 2

[0031]

[0032] 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, 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, dried over Na2SO4, 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 (3a, 38mg, yield: 76%).

[0033] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3a prepared in Example 2 are as follows:

[0034] 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);

[0035] 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;

[0036] HRMS (ESI) calculation for C 14 H 18 NO3 + (M + H) + 248.1281, found 248.1281.

[0037] Example 3

[0038]

[0039] Mes-Acr-Me-ClO4 (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, 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, dried over Na2SO4, 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 (3a, 28mg, yield: 57%).

[0040] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3a prepared in Example 3 are as follows:

[0041] 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);

[0042] 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;

[0043] HRMS (ESI) calculation for C 14 H 18 NO3 + (M + H) + 248.1281, found 248.1281.

[0044] Example 4

[0045]

[0046] Add Ru(bpy)3Cl2 (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, 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, dried over Na2SO4, 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 (3a, 43mg, yield: 87%).

[0047] Example 4 The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the prepared product 3a are as follows:

[0048] 1 H NMR (600 MHz, Chloroform- d ) d7.78–7.76 (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);

[0049] 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;

[0050] HRMS (ESI) calculation for C 14 H 18 NO3 + (M + H) + 248.1281, found 248.1281.

[0051] Example 5

[0052]

[0053] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1b (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and 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, dried over Na2SO4, 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 (3b, 37mg, yield: 71%).

[0054] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3b prepared in Example 5 are as follows:

[0055] 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);

[0056] 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;

[0057] HRMS (ESI) calcd for C 15 H 20 NO3 + (M + H) + 262.1438, found 262.1437.

[0058] Example 6

[0059]

[0060] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1c (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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 the reaction, and ethyl acetate was extracted three times. The combined organic layers were washed once with NaOH solution (1mol / L) and once with saturated brine, dried over Na2SO4, 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 (3c, 40mg, yield: 76%).

[0061] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3c prepared in Example 6 are as follows:

[0062] 1 H NMR (400 MHz, Chloroform- d ) d 7.59 (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);

[0063] 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;

[0064] HRMS (ESI) calculation for C 15 H 20NO3 + (M + H) + 262.1438, found 262.1440.

[0065] Example 7

[0066]

[0067] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1d (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3d, 39mg, yield: 75%).

[0068] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3d prepared in Example 7 are as follows:

[0069] 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);

[0070] 13 C NMR (101 MHz, Chloroform- d ) d167.5, 167.3, 141.8, 138.1, 131.6,129.2, 127.3, 126.8, 61.1, 39.6, 31.8, 21.4, 14.1;

[0071] HRMS (ESI) calculation for C 15 H 19 NO3Na + (M + Na) + 284.1257, found 284.1254.

[0072] Example 8

[0073]

[0074] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1e (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3e, 43mg, yield: 81%).

[0075] The hydrogen spectrum, carbon spectrum, fluorine spectrum and high-resolution mass spectrum data of the product 3e prepared in Example 8 are as follows:

[0076] 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);

[0077] 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;

[0078] 19 F NMR (377 MHz, Chloroform- d ) d -113.30;

[0079] HRMS (ESI) calculation for C 14 H 17 FNO3 + (M + H) + 266.1187, found 266.1190.

[0080] Example 9

[0081]

[0082] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1f (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20: 1 (v / v)) to obtain a colorless oil product (3f, 46mg, yield: 82%).

[0083] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3f prepared in Example 9 are as follows:

[0084] 11H NMR (400 MHz, Chloroform- d ) d 7.71 (d, J J = 8.4 Hz, 2H), 7.39 (d, J J = 8.5Hz, 2H), 6.78 (br s, 1H), 6.25 (s, 1H), 5.69 (s, 1H), 4.23 (q, J J = 7.1 Hz, 2H),3.58 (q, J J = 6.1 Hz, 2H), 2.63 (t, J J = 6.4 Hz, 2H), 1.30 (t, J J = 7.1 Hz, 3H);

[0085] 13 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;

[0086] HRMS (ESI) calcd for C 14 H 17 ClNO3 + (M + H) + 282.0891, found 282.0890.

[0087] Example 10

[0088]

[0089] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1g (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3g, 52mg, yield: 80%).

[0090] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3g prepared in Example 10 are as follows:

[0091] 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);

[0092] 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;

[0093] HRMS (ESI) calculation for C 14 H 17 BrNO3 + (M + H) +326.0386, found 326.0384.

[0094] Embodiment 11

[0095]

[0096] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1h (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 47mg, yield: 77%).

[0097] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3h prepared in Example 11 are as follows:

[0098] 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);

[0099] 13 C NMR (101 MHz, Chloroform- d ) d167.5, 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;

[0100] HRMS (ESI) calculation for C 18 H 26 NO3 + (M + H) + 304.1907, found 304.1907.

[0101] Example 12

[0102]

[0103] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1i (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, filtered and concentrated, and further separated and purified by column chromatography (eluent: petroleum ether: ethyl acetate = 20: 1 (v / v)) to obtain a white solid product (3i, 52mg, yield: 83%, melting point: 69-70°C).

[0104] The hydrogen spectrum, carbon spectrum, fluorine spectrum and high-resolution mass spectrum data of the product 3i prepared in Example 12 are as follows:

[0105] 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);

[0106] 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;

[0107] 19 F NMR (377 MHz, Chloroform-d) d -62.9;

[0108] HRMS (ESI) calculation for C 15 H 17 F3NO3 + (M + H) + 316.1155, found 316.1154.

[0109] Embodiment 13

[0110]

[0111] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1j (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3j, 46mg, yield: 80%).

[0112] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3j prepared in Example 13 are as follows:

[0113] 1 H NMR (400 MHz, Chloroform- d ) d 7.96 (d, J J = 8.1 Hz, 2H), 7.84 (d, J J = 8.2Hz, 2H), 6.99 (br s, 1H), 6.24 (s, 1H), 5.69 (s, 1H), 4.21 (q, J J = 7.1 Hz, 2H),3.59 (q, J J = 6.1 Hz, 2H), 2.63 (t, J J = 6.7 Hz, 2H), 2.60 (s, 3H), 1.29 (t, J J = 7.1Hz, 3H);

[0114] 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;

[0115] HRMS (ESI) calcd for C 16 H 20 NO4 + (M + H) + 290.1387, found 290.1387.

[0116] Example 14

[0117]

[0118] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1k (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 47mg, yield: 85%).

[0119] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3k prepared in Example 14 are as follows:

[0120] 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);

[0121] 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;

[0122] HRMS (ESI) calculation for C 16 H 22 NO3 + (M + H) + 276.1594, found 276.1595.

[0123] Embodiment 15

[0124]

[0125] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1l (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3l, 51mg, yield: 75%).

[0126] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 31 prepared in Example 15 are as follows:

[0127] 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);

[0128] 13 C NMR (151 MHz, Chloroform- d ) d 167.7, 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;

[0129] HRMS (ESI) calculation for C 17 H 24NO6 + (M + H) + 338.1598, found 338.1595.

[0130] Example 16

[0131]

[0132] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1m (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 46mg, yield: 78%).

[0133] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3m prepared in Example 16 are as follows:

[0134] 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);

[0135] 13C 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;

[0136] HRMS (ESI) calculation for C 18 H 20 NO3 + (M + H) + 298.1438, found 298.1436.

[0137] Embodiment 17

[0138]

[0139] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1n (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3n, 39mg, yield: 79%).

[0140] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3n prepared in Example 17 are as follows:

[0141] 1 H 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);

[0142] 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.

[0143] HRMS (ESI) calculation for C 13 H 17 N2O3 + (M + H) + 249.1234, found 249.1238.

[0144] Embodiment 18

[0145]

[0146] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1o (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3o, 35mg, yield: 74%).

[0147] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3o prepared in Example 18 are as follows:

[0148] 1¹H NMR (600 MHz, Chloroform- d ) d 7.45 (s, 1H), 7.12 (d, J J = 3.3 Hz, 1H),6.62 (br s, 1H), 6.51 (dd, J J = 3.4, 1.7 Hz, 1H), 6.29 (s, 1H), 5.69 (s, 1H),4.25 (q, J J = 7.1 Hz, 2H), 3.61 (q, J J = 6.5 Hz, 2H), 2.64 (t, J J = 6.7 Hz, 2H), 1.34(t, J J = 7.1 Hz, 3H);

[0149] 13 ¹³C 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;

[0150] HRMS (ESI) calcd for C 12 H 16 NO4 + (M + H) + 238.1074, found 238.1075.

[0151] Example 19

[0152]

[0153] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1o (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 40mg, yield: 80%).

[0154] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3p prepared in Example 19 are as follows:

[0155] 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);

[0156] 13 C NMR (101 MHz, Chloroform- d ) d 167.6, 161.8, 139.1, 138.0, 129.7,127.8, 127.5, 127.5, 61.1, 39.7, 31.8, 14.1;

[0157] HRMS (ESI) calculation for C 12 H 16 NO3S + (M + H)+ 254.0846 found 254.0849.

[0158] Embodiment 20

[0159]

[0160] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1q (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 32mg, yield: 70%).

[0161] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3q prepared in Example 20 are as follows:

[0162] 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);

[0163] 13 C NMR (101 MHz, Chloroform- d ) d175.0, 167.2, 137.9, 127.0, 61.0,39.9, 38.6, 31.9, 25.3, 18.1, 14.2;

[0164] HRMS (ESI) calculation for C 12 H 20 NO3 + (M + H) + 226.1438, found 226.1438.

[0165] Embodiment 21

[0166]

[0167] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1r (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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 (3r, 35mg, yield: 69%).

[0168] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3r prepared in Example 21 are as follows:

[0169] 1 H NMR (400 MHz, Chloroform- d ) d 6.22 (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);

[0170] 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;

[0171] HRMS (ESI) calculation for C 14 H 24 NO3 + (M + H) + 254.1751, found 254.1751.

[0172] Embodiment 22

[0173]

[0174] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1s (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 41mg, yield: 74%).

[0175] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3s prepared in Example 22 are as follows:

[0176] 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);

[0177] 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;

[0178] HRMS (ESI) calculation for C 15 H 20 NO4 + (M + H) + 278.1387, found 278.1387.

[0179] Embodiment 23

[0180]

[0181] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1t (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 33mg, yield: 61%).

[0182] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3t prepared in Example 23 are as follows:

[0183] 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);

[0184] 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;

[0185] HRMS (ESI) calculation for C 16 H 20 NO3 + (M + H) + 274.1438, found 274.1439.

[0186] Embodiment 24

[0187]

[0188] Ru(bpy)3Cl2 (0.004mmol, 2mol%) and 1u (0.4mmol) were added to a dry Schlenk tube, and then ethyl 2-((phenylsulfonyl)methyl)acrylate (2a, 0.2mmol), triethylamine (0.4mmol), and acetonitrile (2.0mL, 0.1M) were added under a 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, dried over Na2SO4, 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, 45mg, yield: 60%).

[0189] The hydrogen spectrum, carbon spectrum and high-resolution mass spectrum data of the product 3u prepared in Example 24 are as follows:

[0190] 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);

[0191] 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;

[0192] HRMS (ESI) calculation for C 24 H 30 NO3 + (M + H) + 380.2220, found 380.2220.

[0193] 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 N -A method for preparing a butenyl amide compound, characterized in that: Will 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 -Butenylamide compounds; 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, Ar is 4-nitrophenyl; The organic solvent is N , N - dimethylacetamide; The base is triethylamine; The wavelength of the light is 460 nm.

2. The preparation method according to claim 1, characterized in that: The free radical initiator is 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, Ru(PPh3)3Cl2 or more.

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

1.

4. 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.

Images