A method for selenylation, amination of olefins under mild electrochemical conditions

Abstract

This invention discloses a novel method for achieving the amino- and selenium-functionalization of styrene by providing a nitrogen source after decarboxylation and decarbonization of an N-phenylglycine derivative under electrochemical conditions. The method involves reacting a styrene derivative, an N-phenylglycine derivative, and a diphenyldiselenoether derivative at 30°C for 2–4 hours under constant current conditions in the presence of an electrolyte, yielding an aminoselenoylated olefin derivative in a one-pot reaction. This method eliminates the need for transition metals and hazardous peroxides, reducing costs and potential safety risks. It offers excellent yields, uses inexpensive raw materials, is simple to operate, and has a wide substrate adaptability. Furthermore, this reaction can be scaled up to gram-scale reactions, demonstrating potential for industrial applications.

Description

Technical Field

[0001] This invention relates to a method for achieving bifunctionalization of olefins through selenization and amination, and particularly to a method for bifunctionalization of olefins through selenization and amination without the involvement of transition metals under electrochemical conditions, belonging to the fields of pharmaceutical intermediate synthesis and fine organic synthesis. Background Technology

[0002] Selenium is an essential trace element for the human body and plays an important role in human metabolic health. Therefore, organoselenium compounds are considered a promising drug molecule, as selenium is found in many common drugs for antitumor, antioxidation, antifibrinolysis, antiparasitic, antibacterial, and antidepressant purposes (as shown below) [Tobe T, Ueda K, Ando M, et al. Thiol-mediated multiple mechanisms centered on selenodiglutathione determines elenium cytotoxicity against MCF-7 cancer cells[J]. Journal of Biological Inorganic Chemistry, 2015, 20: 687-694.;Macegoniuk K, Grela E, Palus J, et al. 1,2-Benzisoselenazol-3(2H)-one derivatives as a new class of bacterial urease inhibitors[J]. Journal of Medicinal Chemistry, 2016, 59(17): 8125-8133.;Nascimento V, Alberto EE, Tondo DW, et al. GPx-like Activity of selenides and selenoxides: experimental evidence for the involvement of hydroxy perhydroxyselenane as the active species [J]. Journal of the American Chemical Society, 2012, 134(1): 138-141. Reported methods for the bifunctionalization of olefins through selenization and amination include: Ca(NTF2)2-catalyzed olefin amination and oxyselenization methods [Kuang M, Li H, Zeng Z, et al. Calcium(II)-mediated three-component selenofunctionalization of alkenes under mild conditions [J].Organic Letters, 2023, 25(45): 8095-8099; Under mild conditions, using K2S2O8 as a catalyst, a method for achieving the bifunctionalization of olefin selenization and amination was developed [Sun K, Wang X, Li G, et al. Peroxodisulfate-mediated selenoamination of alkenes yielding amidoselenide-containing sulfamides and azoles[J]. Chemical Communications, 2016, 52(54): 8471-8474]; A method for achieving β-aminoseleno(sulfurization) of olefins under microwave irradiation using I2 as a catalyst and DMSO as an oxidant [Gomes LS, Neto JSS, Leo ID, et al. Ecofriendly aminochalcogenation of alkenes: a green alternative to obtain compounds with potential anti-SARS-CoV-2 activity[J]. New Journal ofChemistry,2023,47(14):6591-6601.]; Visible-light-induced three-component reaction realizes the intermolecular aminoselenation reaction of alkenes with sulfonamides and diselen ethers [Liu GQ,Zhou CF,Zhang YQ,et al.Visible-light-induced intermolecular aminoselenation of alkenes[J].Green Chemistry,2021,23(24):9968-9973]; A method to realize aminoselenation and oxyselenation of alkenes under electrochemical conditions without transition metal catalysts and additional oxidants [Wang R,Zhang N,Zhang Y,et al.Versatile electrooxidative amino-and oxyselenation of alkenes[J].Green Chemistry,2023,25(10):3925-3930. Traditional methods often require stringent reaction conditions, such as metal catalysis, high temperatures, pre-prepared reactants, and complex operations. They also suffer from narrow substrate applicability and high costs. Therefore, developing a method for the bifunctionalization of olefins through selenization and amination using readily available raw materials, simple operation, and low cost has significant theoretical and practical value.

[0003] Summary of the Invention

[0004] To address the shortcomings of existing methods for the selenization and amination of olefins, such as the need for irritating or toxic reagents, harsh reaction conditions, or pre-functionalized substrates, this invention provides a novel method for the difunctionalization of styrene into amino and selenyl groups by providing a nitrogen source after decarboxylation and decarbonization of N-phenylglycine derivatives under electrochemical conditions. This method offers advantages such as readily available and inexpensive raw materials, simple operation, rapid reaction, wide substrate adaptability, and air compatibility. Therefore, this method has promising applications in the synthesis of olefin aminoselenization derivatives.

[0005] To achieve the above-mentioned technical objectives, the present invention provides a novel method for realizing the amino and selenium bifunctionalization reaction of styrene by providing a nitrogen source after decarboxylation and decarbonization of N-phenylglycine derivatives under electrochemical conditions. The method is as follows: under electrochemical conditions, styrene of formula 1, N-phenylglycine of formula 2, and diphenyldiselenoether of formula 3 are reacted at 30°C for 2 to 4 hours under constant current conditions in the presence of an electrolyte to obtain aminoselenoyl derivative of formula 4 in one pot.

[0006]

[0007] Wherein, R1 is selected from hydrogen, alkyl, alkoxy, halogen, aryl, acetoxy; R2 is selected from hydrogen, alkyl, halogen, aryl, trifluoromethyloxy, trifluoromethyl, ester; R3 is selected from hydrogen, alkyl; and R4 is selected from aryl, alkyl.

[0008] In a preferred embodiment, the styrene derivative of Formula 1 is styrene, 4-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-phenylstyrene, or 4-acetoxystyrene.

[0009] In a preferred embodiment, the N-phenylglycine derivative described in Formula 2 is N-phenylglycine, (3-fluorophenyl)glycine, (4-fluorophenyl)glycine, (4-chlorophenyl)glycine, (4-bromophenyl)glycine, (4-iodophenyl)glycine, (4-(trifluoromethyl)phenyl)glycine, (4-(trifluoromethoxy)phenyl)glycine, o-tolycine, m-tolycine, [1,1'-biphenyl]-4-ylglycine, phenylphenylalanine, phenylalanine, or phenylvaline.

[0010] In a preferred embodiment, the diselenide derivative described in Formula 3 is diphenyldiselenide, dibenzyldiselenide, or diethyldiselenide;

[0011] In a preferred embodiment, the styrene of Formula 1, the N-phenylglycine of Formula 2, and the diphenyldiselenoether of Formula 3 are electrochemically synthesized into an aminoselenoyl derivative of Formula 4. This aminoselenoyl derivative is N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, 3-fluoro-N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, 4-fluoro-N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, 4-chloro-N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, or 4-bromo-N- (1-Phenylacetyl-2-(phenylselenoyl)ethyl)aniline, 4-iodo-N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, N-(1-phenyl-2-(phenylselenoyl)ethyl)-4-(trifluoromethyl)aniline, N-(1-phenyl-2-(phenylselenoyl)ethyl)-4-(trifluoromethoxy)aniline, 2-methyl-N-(1-phenyl-2-(phenylselenoyl)aniline, 3-methyl-N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, N-(1-phenyl-2-(phenylselenoyl)ethyl)aniline, N-(2-(phenylselenoyl)-1-(o-tolyl)ethyl)aniline, N-(2-(phenylselenoyl)-1-(m-tolyl)ethyl)aniline, N-(2-(phenylselenoyl)-1-(p-tolyl)ethyl)aniline, N-(1-(4-methoxyphenyl)-2-(phenylselenoyl)ethyl)aniline, N-(1-(4-tert-butylphenyl)-2-(phenylselenoyl)ethyl)aniline, N-(1-(4-acetoxyphenyl)- 2-(phenylselenoyl)ethyl)aniline, N-(1-(4-fluorophenyl)-2-(phenylselenoyl)ethyl)aniline, N-(1-(4-chlorophenyl)-2-(phenylselenoyl)ethyl)aniline, N-(1-(4-bromophenyl)-2-(phenylselenoyl)ethyl)aniline, N-(1-([1,1'-biphenyl]-4-yl)-2-(phenylselenoyl)ethyl)aniline, N-(2-(benzylselenoyl)-1-phenylethyl)aniline, N-(2-(ethylselenoyl)-1-phenylethyl)aniline.

[0012] In a preferred embodiment, the molar amount of styrene in Formula 1 is 0.3 mmol, the molar amount of N-phenylglycine in Formula 2 is 0.3 mmol, and the molar amount of diphenyldiselenic acid in Formula 3 is 0.1 mmol.

[0013] The preferred solutions are 10mA, 12mA, 15mA, and 20mA, with the most preferred solution being 12mA.

[0014] In a preferred embodiment, the reaction time is 2–3.5 hours and the reaction temperature is 0–35°C. In the most preferred embodiment, the reaction time is 2.5 hours and the reaction temperature is 25°C.

[0015] In a preferred embodiment, the electrolyte added to the reaction system is one of the following: potassium iodide, lithium perchlorate, tetrabutylammonium tetrafluoroborate, tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, ammonium iodide, sodium iodide, elemental iodine, tetrabutylammonium bromide, and potassium chloride. Tetramethylammonium iodide is the most preferred.

[0016] In a preferred embodiment, the molar amount of tetramethylammonium iodide added to the reaction system is 1 to 1.5 times that of styrene of Formula 1. In the most preferred embodiment, the molar amount of tetramethylammonium iodide added to the reaction system is 1.25 times that of styrene of Formula 1.

[0017] In a preferred embodiment, the solvent for the reaction is one of acetonitrile + water, sulfolane + water, water, N,N-dimethylformamide + water, ethyl acetate + water, acetonitrile, petroleum ether + water, tetrahydrofuran + water, dichloromethane + water, methanol + water, or 1,2-dichloroethane + water. In the most preferred embodiment, the solvent for the reaction is dichloromethane + water.

[0018] In a preferred embodiment, the amount of solvent added to the reaction system is 2-4 mL. In the most preferred embodiment, the amount of solvent used in the reaction system is dichloromethane (2 mL) + water (2 mL).

[0019] In preferred embodiments, the electrodes used in the reaction are platinum(+) / platinum(-), platinum(+) / carbon(-), carbon(+) / platinum(-), carbon(+) / nickel(-), carbon(+) / / silver(-), carbon(+) / iron(-), carbon(+) / aluminum(-), carbon(+) / zinc(-), carbon(+) / copper(-), and carbon(+) / magnesium(-). In the most preferred embodiment, the electrode used in the reaction is carbon(+) / platinum(-).

[0020] The preferred scheme is to use an atmosphere of O2, N2, or air, with the most preferred scheme being an air atmosphere.

[0021] The equations for achieving the bifunctionalization of olefin selenization and amination in this invention are as follows.

[0022]

[0023] Based on extensive experimental findings and reference to previous literature, this invention proposes the following reasonable reaction mechanism.

[0024] First, the iodide anion is oxidized at the anode, losing electrons to form an iodide free radical. This free radical couples to yield elemental iodine. The nascent elemental iodine rapidly combines with the carboxyl anion A from the ionization of amino acids to form an iodo-oxyonium salt B, releasing one molecule of iodide anion. The unstable iodo-oxyonium salt B readily undergoes homolytic cleavage of the iodoxy bond, generating a carboxyl radical intermediate C and an iodide free radical that can return to the cycle. The carboxyl radical intermediate C undergoes decarboxylation, releasing one molecule of carbon dioxide and generating a carbon free radical D. Carbon free radical D then reacts with the iodide at the anode... Electron loss at the anode yields an imine cation intermediate E. The imine hydrolyzes to give aniline and intermediate G. Intermediate G is deprotonated to formaldehyde. Simultaneously, diphenyldiselenoether loses electrons at the anode to generate a selenium radical cation H. Selenium radical cation H dissociates into a selenium cation I and a selenium radical J. Selenium cation I reacts with styrene via an electrophilic addition reaction to generate a cyclic selenium cation intermediate K. Then, aniline and the cyclic selenium cation intermediate K undergo a nucleophilic reaction to lose hydrogen and generate the target compound 6. At the cathode, hydrogen ions gain electrons to generate hydrogen gas.

[0025] In addition, carbon radical D can be converted into nitrogen radical F via 1,2-H migration. After gaining electrons at the cathode, nitrogen radical F nucleophilically attacks cycloselenic cation intermediate K to obtain byproduct I; or water in the system directly nucleophilically attacks cycloselenic cation intermediate K, losing one molecule of hydrogen to obtain byproduct II.

[0026]

[0027] The synthetic method for achieving the bifunctionalization of olefins through selenization and amination according to the present invention includes the following steps:

[0028] Styrene derivative (0.3 mmol), amino acid derivative (0.3 mmol), selenide derivative (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H2O (2 mL) were added to a 10 mL three-necked flask. A carbon rod electrode (5 mm * 85 mm) was used as the anode (immersion surface area 8 * 5 mm). 2 A Pt electrode (10mm*15mm*0.1mm) is used as the cathode (immersion surface area 10*10mm). 2 The electrodes were inserted into both sides of a three-necked flask, and a reaction current of 12 mA was applied. The mixture was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction solution was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain the mixture. Finally, the mixture was purified by thin-layer chromatography or column chromatography (silica gel, petroleum ether / ethyl acetate).

[0029] Compared with the prior art, the technical solution of the present invention has the following advantages and effects:

[0030] This invention develops a bifunctionalization reaction of styrene under electrochemical conditions involving amination and selenization. In this reaction, the decarboxylation and decarbonylation fragment of N-phenylglycine serves as the amino source, and diphenyldiselenoether serves as the selenium source. This method utilizes inexpensive and readily available raw materials, is simple to operate, reacts rapidly, and has broad substrate applicability; in addition to amino acids, primary and secondary amines are also suitable for this reaction system. Furthermore, amino acids can be derived from the recycling of protein-rich biomass, providing a new approach for the sustainable development of related chemical industries and alleviating the energy crisis. Therefore, this synthetic method is a green and environmentally friendly approach. Attached Figure Description

[0031] 【 Figure 1 [This refers to the product obtained in Example 1] 1 H NMR spectrum;

[0032] 【 Figure 2 [This refers to the product obtained in Example 1] 13 C NMR spectrum;

[0033] 【 Figure 3 [This refers to the product obtained in Example 4] 1 H NMR spectrum;

[0034] 【 Figure 4 [This refers to the product obtained in Example 4] 13 C NMR spectrum. Detailed Implementation

[0035] The present invention will be further described in detail below with reference to the specific embodiments and accompanying drawings. The processes, conditions, reagents, and test methods for implementing the present invention, except as specifically mentioned below, are all common knowledge and general information in the art, and the present invention does not have any particular limitations.

[0036] Example 1

[0037] In a 10 mL three-necked flask, styrene (0.3 mmol), N-phenylglycine (0.3 mmol), diphenyldiselenoether (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under reduced pressure in a vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 71% (50.2 mg). 1 H NMR(400MHz,Chloroform-d)δ7.60-7.49(m,2H),7.42-7.26(m,8H),7.11(t,J=7.9Hz,2H),6.71(t,J=7.3Hz ,1H),6.49(d,J=8.0Hz,2H),4.58-4.45(m,2H),3.40(dd,J=12.6,4.5Hz,1H),3.24(dd,J=12.6,8.9Hz,1H); 13 C NMR (101MHz, Chloroform-d) δ147.13,142.73,133.60,129.38,129.35,129.15,128.90,127.62,127.59,126.38,117.86,113.78,57.88,36.55.

[0038] Example 2

[0039] In a 10 mL three-necked flask, styrene (0.3 mmol), (3-fluorophenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Yellow liquid, yield 61% (45.3 mg). 1 HNMR(400MHz,Chloroform-d)δ7.52(dd,J=7.0,2.2Hz,2H),7.34-7.25(m,8H),6.99(q,J=7.7Hz,1H),6.34(td,J=8.4,2.4Hz,1H),6.22(dd,J=8. 1,2.3Hz,1H),6.08(dt,J=11.6,2.4Hz,1H),4.57(s,1H),4.40(dd,J=9.1,4.5Hz,1H),3.35(dd,J=12.7,4.5Hz,1H),3.17(dd,J=12.7,9.0Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ163.84(d, 1 J C-F =243.9Hz), 148.88(d, 3 J C-F =10.8Hz),142.15,133.72,130.13(d, 3 J C-F =10.2Hz),129.38,129.02,128.96,127.76,127.74,126.25,109.57(d, 4 J C-F =2.3Hz), 104.29(d, 2 J C-F =21.5Hz),100.49(d,J=25.6Hz),57.85,36.32; 19 F NMR(376MHz,Chloroform-d)δ-112.79.

[0040] Example 3

[0041] In a 10 mL three-necked flask, styrene (0.3 mmol), (4-fluorophenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 82% (60.9 mg). 1 HNMR(400MHz,Chloroform-d)δ7.58-7.52(m,2H),7.39-7.24(m,8H),6.85-6.76(m,2H),6.44 -6.36(m,2H),4.52-4.32(m,2H),3.39(dd,J=12.8,4.3Hz,1H),3.19(dd,J=12.6,9.1Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ156.03(d, 1 J C-F =236.4Hz), 143.50(d, 4 J C-F =1.9Hz),142.56,133.66,129.37,129.17,128.94,127.70,127.67,126.35,115.50(d, 3 J C-F =22.4Hz), 114.64(d, 2 J C-F =7.4Hz), 58.40, 36.60; 19 F NMR(376MHz,Chloroform-d)δ-127.40.

[0042] Example 4

[0043] In a 10 mL three-necked flask, styrene (0.3 mmol), (4-chlorophenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 78% (59.1 mg). 1 HNMR(400MHz,Chloroform-d)δ7.61-7.48(m,2H),7.42-7.20(m,8H),7.02(dd,J=8.8,2.4Hz,2H),6. 37(dd,J=8.7,2.3Hz,2H),4.64-4.30(m,2H),3.37(ddd,J=12.7,4.4,1.9Hz,1H),3.23-3.13(m,1H); 13 C NMR (101MHz, Chloroform-d) δ145.67,142.23,133.74,129.41,129.05,128.98,128.96,127.77,127.75,126.29,122.46,114.86,57.92,36.43.

[0044] Example 5

[0045] In a 10 mL three-necked flask, styrene (0.3 mmol), (4-bromophenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Light brown liquid, yield 78% (59.1 mg). 1 HNMR(400MHz,Chloroform-d)δ7.61-7.51(m,2H),7.41-7.24(m,8H),7.18(dd,J=8.7,2.7Hz,2H),6.35(dd,J=8.8,2. 8Hz,2H),4.56(s,1H),4.43(dt,J=8.5,3.6Hz,1H),3.40(dt,J=12.9,3.3Hz,1H),3.20(ddd,J=12.5,8.7,2.3Hz,1H); 13 C NMR (101MHz, Chloroform-d) δ146.12,142.19,133.77,131.87,129.45,129.11,129.02,127.82,127.79,126.33,115.40,109.62,57.87,36.42.

[0046] Example 6

[0047] In a 10 mL three-necked flask, styrene (0.3 mmol), (4-iodophenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Light brown liquid, yield 48% (46.1 mg). 1 HNMR (400MHz, Chloroform-d) δ7.53 (td, J=4.5, 4.1, 2.3Hz, 2H), 7.34-7.27 (m, 10H), 6.22 (dd, J=8. 7,4.0Hz,2H),4.63-4.34(m,2H),3.36(dt,J=12.7,3.8Hz,1H),3.17(ddd,J=12.3,8.8,3.1Hz,1H); 13 C NMR (101MHz, Chloroform-d) δ146.64,142.09,137.67,133.74,129.40,129.02,128.97,127.77,127.75,126.26,115.98,78.79,57.69,36.35.

[0048] Example 7

[0049] In a 10 mL three-necked flask, styrene (0.3 mmol), (4-(trifluoromethyl)phenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Yellow liquid, yield 31% (26.1 mg). 1 H NMR(400MHz,Chloroform-d)δ7.57-7.50(m,2H),7.36-7.26(m,8H),6.93(d,J=8.5Hz,2H),6.42-6.36(m, 2H), 4.57 (s, 1H), 4.39 (dd, J = 9.2, 4.4Hz, 1H), 3.37 (dd, J = 12.7, 4.3Hz, 1H), 3.18 (dd, J = 12.7, 9.2Hz, 1H); 13 C NMR(101MHz,Chloroform-d)δ145.90,142.23,140.75,133.70,133.65,129.37,128.98,127.78,127.73,126.25,122.23,

[0050] 120.68(d, 1 J C-F =256.1Hz),113.99,58.11,36.42; 19 F NMR(376MHz,Chloroform-d)δ-58.40.

[0051] Example 8

[0052] In a 10 mL three-necked flask, styrene (0.3 mmol), (4-(trifluoromethoxy)phenyl)glycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under reduced pressure in a vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 43% (37.6 mg). 1 H NMR(400MHz,Chloroform-d)δ7.52(dd,J=7.5,2.1Hz,2H),7.36-7.26(m,8H),6.91(d,J=8.5Hz,2H),6.41-6.3 4(m,2H),4.55(s,1H),4.37(dd,J=9.2,4.3Hz,1H),3.36(dd,J=12.7,4.3Hz,1H),3.16(dd,J=12.7,9.1Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ145.88,142.22,140.76,133.68,131.53,129.34,128.98,128.95,127.74(d, 3 J C-F =5.1Hz),126.23,122.20,120.65(d, 1 J C-F =256.3Hz),113.98,58.11,36.40; 19 F NMR(376MHz,Chloroform-d)δ-58.44.

[0053] Example 9

[0054] In a 10 mL three-necked flask, styrene (0.3 mmol), o-tolylglycine (0.3 mmol), diphenyldiselenoether (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 30% (22.1 mg). 1 H NMR(400MHz,Chloroform-d)δ7.58-7.52(m,2H),7.42-7.26(m,8H),7.09(d,J=7.3Hz,1H),6.94(t,J=7.8Hz,1H),6.66 (t,J=7.4Hz,1H),6.27(d,J=8.1Hz,1H),4.59-4.37(m,2H),3.47(dd,J=12.6,4.4Hz,1H),3.31(dd,J=12.6,8.9Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ145.04,142.82,133.23,130.03,129.43,129.38,128 .92,127.59,127.50,126.93,126.33,122.64,117.44,111.44,57.59,36.81,17.64.

[0055] Example 10

[0056] In a 10 mL three-necked flask, styrene (0.3 mmol), m-tolueneglycine (0.3 mmol), diphenyldiselenoether (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 45% (33.1 mg). 1 H NMR(400MHz,Chloroform-d)δ7.57-7.51(m,2H),7.39-7.26(m,8H),6.97(td,J=7.8,2.0Hz,1H),6.52(d,J=7.5Hz, 1H),6.33(s,1H),6.25(d,J=8.2Hz,1H),4.59-4.35(m,2H),3.37(ddd,J=12.5,4.8,1.7Hz,1H),3.28-3.19(m,1H); 13 C NMR(101MHz,Chloroform-d)δ147.09,142.77,138.86,133.52,129.45,129.31,129 .01,128.86,127.56,127.51,126.37,118.80,114.60,110.72,57.80,36.46,21.65.

[0057] Example 11

[0058] In a 10 mL three-necked flask, styrene (0.3 mmol), [1,1'-biphenyl]-4-ylglycine (0.3 mmol), diphenyldiselenes (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 18:1). Pale yellow liquid, yield 41% (35.2 mg). 1 H NMR(400MHz,Chloroform-d)δ7.61(d,J=7.3Hz,2H),7.54(t,J=7.5Hz,2H),7.48-7.23(m,11H),7.16(dd,J=7.5,1.7Hz,1H),7.07(td,J=7.9,1.7Hz,1 H),6.78(t,J=7.4Hz,1H),6.38(d,J=8.1Hz,1H),4.90(s,1H),4.53(dd,J=9 .0,4.6Hz,1H),3.33(dd,J=12.4,4.6Hz,1H),3.13(dd,J=12.4,8.8Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ143.80,142.66,139.41,133.35,130.26,129.61,129.58,129.20, 129.03,128.88,128.52,128.26,127.58,127.41,127.36,126.28,117.44,111.94,57.42,36.83.

[0059] Example 12

[0060] In a 10 mL three-necked flask, 0.3 mmol of 2-methylstyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenes, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 60% (44.1 mg). 1 H NMR(400MHz,Chloroform-d)δ7.61(td,J=4.9,2.4Hz,2H),7.54-7.49(m,1H),7.40-7.31(m,3H),7.25-7.05(m,5H),6.74(d, J=4.8Hz,1H),6.49-6.43(m,2H),4.71-4.42(m,2H),3.35(dq,J=12.8,2.9,1.8Hz,1H),3.19-3.09(m,1H),2.35-2.25(m,3H); 13 C NMR(101MHz,Chloroform-d)δ147.33,140.39,134.86,134.26,130.94,129.37,129 .25,129.15,127.86,127.42,126.86,125.47,117.86,113.58,54.13,34.83,19.00.

[0061] Example 13

[0062] In a 10 mL three-necked flask, 0.3 mmol of 3-methylstyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenoether, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 70% (51.5 mg). 1 H NMR(400MHz,Chloroform-d)δ7.58(dt,J=7.3,2.4Hz,2H),7.34-7.12(m,9H),6.74(dd,J=8.0,6.7Hz,1H),6. 56-6.49(m,2H),4.60-4.37(m,2H),3.41(dd,J=12.5,4.6Hz,1H),3.26(dd,J=12.6,8.9Hz,1H),2.38(s,3H); 13 C NMR(101MHz,Chloroform-d)δ147.29,142.79,138.55,133.62,129.50,129.37,129 .20,128.82,128.48,127.59,127.04,123.50,117.85,113.81,57.98,36.57,21.68.

[0063] Example 14

[0064] In a 10 mL three-necked flask, 0.3 mmol of 4-methylstyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenoether, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 80% (58.8 mg). 1 H NMR(400MHz,Chloroform-d)δ7.68-7.55(m,2H),7.39-7.27(m,5H),7.24-7.11(m,4H),6.73(t,J=7.2Hz ,1H),6.53(dd,J=8.2,2.5Hz,2H),4.75-4.32(m,2H),3.45-3.37(m,1H),3.32-3.22(m,1H),2.39(s,3H); 13 C NMR (101MHz, Chloroform-d) δ139.73,137.25,133.57,129.61,129.34,129.17,127.53,126.32,117.82,113.81,57.64,36.59,21.24.

[0065] Example 15

[0066] In a 10 mL three-necked flask, 0.3 mmol of 4-methoxystyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenes, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the mixture was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 31% (23.8 mg). 1 H NMR(400MHz,Chloroform-d)δ7.57-7.48(m,2H),7.37-7.18(m,5H),7.08(t,J=7.5Hz,2H),6.89-6.82(m,2H),6.71-6.63(m,1H ),6.46(d,J=7.9Hz,2H),4.44(dd,J=8.7,4.8Hz,1H),3.79(s,3H),3.34(dd,J=12.5,4.7Hz,1H),3.21(dd,J=12.5,8.7Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ158.96,147.13,134.62,133.50,129.43,129.27,129.09,127.48,127.43,117.76,114.20,113.75,57.25,55.29,36.59.

[0067] Example 16

[0068] In a 10 mL three-necked flask, 0.3 mmol of 4-tert-butylstyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenoether, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 77% (63.1 mg). 1 H NMR(400MHz,Chloroform-d)δ7.55(dt,J=7.7,1.9Hz,2H),7.39-7.28(m,7H),7.17-7.09(m,2H), 6.72(t,J=7.3Hz,1H),6.52(d,J=7.9Hz,2H),4.69-4.35(m,2H),3.45-3.25(m,2H),1.35(s,9H); 13 C NMR(101MHz,Chloroform-d)δ150.40,147.24,139.56,133.51,129.62,129.30 ,129.16,127.48,126.05,125.77,117.75,113.75,57.56,36.52,34.58,31.47.

[0069] Example 17

[0070] In a 10 mL three-necked flask, 0.3 mmol of 4-phenylstyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenoether, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 54% (46.5 mg). 1 H NMR(400MHz,Chloroform-d)δ7.63-7.53(m,6H),7.50-7.41(m,4H),7.36(t,J=7.3Hz,1H),7.31-7.27(m,3H),7.13(t,J=7.7Hz,2H), 6.72(t,J=7.3Hz,1H), 6.52(d,J=7.9Hz,2H), 4.54(dd,J=8.9,4.6Hz,2H), 3.43(dd,J=12.6,4.6Hz,1H), 3.27(dd,J=12.6,8.8Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ147.10,141.74,140.81,140.48,133.63,129.34,129. 17,128.82,127.61,127.59,127.33,127.11,126.83,117.92,113.81,57.61,36.50.

[0071] Example 18

[0072] In a 10 mL three-necked flask, 0.3 mmol of 4-acetoxystyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenes, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 66% (54.3 mg). 1 H NMR(400MHz,Chloroform-d)δ7.56-7.50(m,2H),7.37(d,J=8.2Hz,2H),7.29(d,J=6.0Hz,3H),7.14-7.03(m,4H),6.70(t,J=7 .3Hz,1H),6.45(d,J=7.9Hz,2H),4.65-4.33(m,2H),3.36(dd,J=12.7,4.5Hz,1H),3.18(dd,J=12.6,8.9Hz,1H),2.30(s,3H); 13 CNMR(101MHz,Chloroform-d)δ169.55,149.94,146.97,140.24,133.65,129.38 ,129.20,129.16,127.66,127.38,121.93,117.97,113.77,57.41,36.48,21.24.

[0073] Example 19

[0074] In a 10 mL three-necked flask, 0.3 mmol of 4-fluorostyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenes, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the mixture was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Yellow liquid, yield 36% (26.8 mg). 1 HNMR(400MHz,Chloroform-d)δ7.56-7.49(m,2H),7.31(dt,J=17.2,6.1Hz,5H),7.13-7.05(m,2H),7.00(t,J=8.4Hz,2H),6.70(dt,J= 8.6,4.3Hz,1H),6.44(dd,J=8.3,2.5Hz,2H),4.45(dt,J=7.8,3.1Hz,2H),3.34(dd,J=12.7,4.6Hz,1H),3.19(dd,J=12.6,8.7Hz,1H); 13 CNMR(101MHz,Chloroform-d)δ162.13(d, 1 J C-F =246.4Hz), 146.89, 138.33(d, 4 J C-F =3Hz),133.65,129.35,129.14,129.11,127.96,127.78(d, 3 J C-F =21.9Hz), 118.01, 115.71(d, 2 J C-F =21.5Hz),113.77,57.21,36.57; 19 F NMR(376MHz,Chloroform-d)δ-115.00.

[0075] Example 20

[0076] In a 10 mL three-necked flask, 0.3 mmol of 4-chlorostyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenes, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the mixture was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Yellow liquid, yield 34% (26.3 mg). 1 HNMR(400MHz,Chloroform-d)δ7.53(dd,J=7.4,2.0Hz,2H),7.30(d,J=2.9Hz,7H),7.13-7.06(m,2H),6.71(t,J= 7.3Hz,1H),6.44(d,J=8.0Hz,2H),4.60-4.36(m,2H),3.34(dd,J=12.6,4.5Hz,1H),3.18(dd,J=12.7,8.7Hz,1H); 13 C NMR (101MHz, Chloroform-d) δ146.81,141.24,133.71,133.17,129.39,129.18,129.03,127.79,127.73,118.11,113.79,57.27,36.42.

[0077] Example 21

[0078] In a 10 mL three-necked flask, 0.3 mmol of 4-bromostyrene, 0.3 mmol of N-phenylglycine, 0.1 mmol of diphenyldiselenes, 0.25 mmol of tetramethylammonium iodide (1.25 equiv.), 2 mL of DCM, and 2 mL of H₂O were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined and washed with saturated saline solution (10 mL × 3). Then, the organic phase was dried with anhydrous Na₂SO₄ for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). A light brown liquid, yield 30% (25.8 mg). 1 HNMR(400MHz,Chloroform-d)δ7.55-7.48(m,2H),7.44(d,J=8.4Hz,2H),7.32-7.27(m,3H),7.23(d,J=8.2Hz,2H),7.10(t,J=7.7H z,2H),6.70(t,J=7.3Hz,1H),6.43(d,J=7.9Hz,2H),4.60-4.33(m,2H),3.33(dd,J=12.7,4.5Hz,1H),3.17(dd,J=12.7,8.8Hz,1H); 13 CNMR(101MHz,Chloroform-d)δ146.78,141.77,133.71,131.96,129.39,129.18,128.99,128.16,127.74,121.29,118.12,113.78,57.32,36.35.

[0079] Example 22

[0080] In a 10 mL three-necked flask, styrene (0.3 mmol), N-phenylglycine (0.3 mmol), dibenzyl diselenyl ether (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 41% (30.1 mg). 1 H NMR(400MHz,Chloroform-d)δ7.37-7.24(m,10H),7.15-7.06(m,2H),6.69(td,J=7.6,7.2,3.5Hz,1H),6.52- 6.45(m,2H),4.42(ddd,J=8.3,4.8,2.6Hz,2H),3.66(t,J=2.1Hz,2H),3.03-2.96(m,1H),2.91-2.81(m,1H); 13 C NMR(101MHz,Chloroform-d)δ147.23,142.90,139.03,129.17,129.07,128.87,128.73,127.55,127.06,126.44,117.81,113.86,57.11,32.38,27.62.

[0081] Example 23

[0082] In a 10 mL three-necked flask, styrene (0.3 mmol), N-phenylglycine (0.3 mmol), diethyldiselenoether (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 10 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 10 mL × 3). The organic phases were combined, and the organic phases were washed with saturated saline solution (10 mL × 3). Then, the organic phases were dried with anhydrous Na₂SO₄ for 10 min, and concentrated under vacuum to obtain the mixture. Finally, the pure product was obtained by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 30% (18.3 mg). 1 H NMR(400MHz,Chloroform-d)δ7.40(d,J=7.1Hz,2H),7.34(t,J=7.4Hz,2H),7. 31-7.24(m,1H),7.15-7.06(m,2H),6.68(t,J=7.3Hz,1H),6.55(d,J=7.9Hz,2 H),4.62(s,1H),4.47(dd,J=8.6,4.7Hz,1H),3.10(dd,J=12.6,4.6Hz,1H),2. 91(dd,J=12.6,8.5Hz,1H),2.49(qd,J=7.5,5.0Hz,2H),1.36(t,J=7.5Hz,3H); 13 C NMR (101MHz, Chloroform-d) δ147.37,143.08,129.22,128.91,127.56,126.41,117.90,113.94,57.26,32.17,17.87,15.82.

[0083]

[0084] Control groups 1–32:

[0085] In a 10 mL three-necked flask, styrene (0.3 mmol), N-phenylglycine (0.3 mmol), diphenyldiselenoether (0.1 mmol), tetramethylammonium iodide (0.25 mmol, 1.25 equiv.), DCM (2 mL), and H₂O (2 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 2.5 h. Finally, the pure product was separated by thin-layer chromatography (ethyl acetate: petroleum ether = 20:1), and the yield was calculated. The specific reaction conditions for each control group are shown in Table 1.

[0086] Table 1. Control group experiments of olefin selenization and amination difunctionalization reactions.

[0087]

[0088]

[0089]

[0090] As can be seen from the table above, time has a certain impact on the reaction, with the best reaction effect achieved at 2.5 hours.

[0091] As can be seen from the table above, the type of electrolyte has a significant impact on the reaction, with tetramethylammonium iodide being the electrolyte with the best reaction effect.

[0092] As can be seen from the table above, the amount of electrolyte has a certain impact on the reaction, with the best reaction effect achieved at 1.25 equivalents.

[0093] As can be seen from the table above, the type of solvent has a significant impact on the reaction, and the solvent with the best reaction effect is dichloromethane (2) + water (2).

[0094] As can be seen from the table above, the type of electrode has a certain influence on the reaction, and the electrode with the best reaction effect is carbon (+) / platinum (-).

[0095] Control group 24:

[0096] In a 250 mL three-necked flask, styrene (4.5 mmol), N-phenylglycine (4.5 mmol), diphenyldiselenoether (1.5 mmol), tetramethylammonium iodide (5.6 mmol, 1.25 equiv.), CH3CN (30 mL), and H2O (30 mL) were added. A carbon rod electrode was used as the anode, and a Pt electrode was used as the cathode, inserted into both sides of the three-necked flask. A reaction current of 12 mA was applied, and the reaction was stirred in an oil bath at 25 °C for 16 h. After the reaction was complete, the electrodes were removed, and the reaction mixture was transferred to a separatory funnel. 60 mL of saturated saline solution was added to the mixture, and then the mixture was extracted with dichloroethane (DCM, 100 mL × 3). The organic phases were combined and washed with saturated saline solution (100 mL × 3). Then, the organic phase was dried with anhydrous Na2SO4 for 10 min and concentrated under vacuum to obtain a mixture. Finally, the pure product was obtained by column chromatography (ethyl acetate: petroleum ether = 20:1). Pale yellow liquid, yield 48% (50.2 mg).

[0097]

[0098] This shows that even when the reaction is scaled up to the gram level, it still has a moderate yield and good prospects for industrial application.

Claims

1. An electrochemical synthesis method for compound of formula 4 under electrochemical conditions, characterized in that: Compounds of Formula 1, Formula 2, and Formula 3 were reacted under constant current conditions in the presence of an electrolyte at 0–35 °C to obtain compound of Formula 4 in a one-pot reaction. Wherein, R1 is selected from hydrogen, alkyl, alkoxy, halogen, aryl, acetoxy; R2 is selected from hydrogen, alkyl, halogen, aryl, trifluoromethyloxy, trifluoromethyl, ester; R3 is selected from hydrogen, alkyl; R4 is selected from aryl, alkyl; the electrolyte is selected from Me4NI, KI, NaI, Et4NI; the selected current intensity is 10mA, 12mA, 15mA, 20mA; the solvent is selected from CH3CN, H2O, a mixture of CH3CN and H2O, a mixture of ethyl acetate (EA) and water, a mixture of petroleum ether (PE) and water, a mixture of dichloromethane (DCM) and water, and a mixture of dichloroethane (DCE) and water.

2. The electrochemical synthesis method of compound 4 under electrochemical conditions according to claim 1, characterized in that: The compound of Formula 1 is one of styrene, 4-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-phenylstyrene, and 4-acetoxystyrene; the compound of Formula 2 is one of N-phenylglycine, (3-fluorophenyl)glycine, (4-fluorophenyl)glycine, (4-chlorophenyl)glycine, (4-bromophenyl)glycine, (4-iodophenyl)glycine, (4-(trifluoromethyl)phenyl)glycine, (4-(trifluoromethoxy)phenyl)glycine, o-tolylglycine, m-tolylglycine, [1,1'-biphenyl]-4-ylglycine, phenylphenylalanine, phenylalanine, and phenylvaline; the compound of Formula 3 is one of diphenyldiselenoether, dibenzyldiselenoether, and diethyldiselenoether.

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