Electrocatalytic synthesis of beta-amino ketones

Abstract

This invention discloses an electrophotocatalytic synthesis method for β-aminoketone compounds, belonging to the field of electrophotocatalytic organic synthesis technology. The electrophotocatalytic synthesis method of this invention employs an electrophotocatalytic strategy to promote the ring-opening functionalization reaction of arylcyclopropane, achieving a one-step, highly efficient synthesis of β-aminoketone compounds. The electrophotocatalytic synthesis method of this invention features mild reaction conditions, requires no addition of stoichiometric chemical oxidants, is simple to operate, and has high synthesis efficiency. Furthermore, the reaction system exhibits good functional group tolerance, compatible with various functional groups, heterocycles, and complex structural substrates, demonstrating promising application prospects and widespread value in organic synthesis, drug synthesis, and medicinal chemistry.

Description

Technical Field

[0001] This invention relates to the fields of electro-photocatalysis and organic synthesis. More specifically, this invention relates to an electro-photocatalytic synthesis method for β-aminoketone compounds. Background Technology

[0002] β-Aminoketones are a class of key nitrogen-containing organic intermediates widely used in the total synthesis of natural products and the construction of drug molecules, and are also the core scaffold structure of many active drug molecules. Currently, the mainstream synthetic routes for β-aminoketones are mainly divided into three categories: Mannich reaction, azaMichael addition reaction, and cyclopropane ring-opening addition reaction.

[0003] Among these, the Mannich reaction, with its advantages of inexpensive and readily available raw materials and simple operation, has become the most widely used preparation method in laboratory research and industrial production. However, this reaction has significant limitations: the reaction conditions are harsh and severe, it has poor compatibility with aromatic amine substrates, and the conventional catalysts have high toxicity, which does not conform to the current development concept of green chemistry and environmental protection requirements. Although the azaMichael addition reaction has the advantage of mild reaction conditions, the α,β-unsaturated ketones are prone to self-polymerization, and primary amine substrates are also prone to initiating double addition side reactions, which significantly reduce the yield and reaction selectivity of the target product.

[0004] The ring-opening addition reaction of cyclopropane is an emerging synthetic strategy in recent years. However, most existing reaction systems still require stoichiometric acid reagents or transition metal complexes, resulting in problems such as high catalyst consumption and insufficient atom economy. Although some studies have circumvented the use of stoichiometric catalysts through electrocatalysis, effectively optimizing the reaction system, the substrate applicability of this improved scheme is narrow, limiting its versatility and promotional value.

[0005] In summary, developing a novel β-aminoketone synthesis process with mild reaction conditions, excellent atom utilization, and broad substrate applicability is a technical challenge that urgently needs to be overcome in this field. Summary of the Invention

[0006] This invention provides an electro-photocatalytic synthesis method for β-amino ketone compounds. The method employs an electro-photocatalytic strategy to induce the ring-opening functionalization reaction of arylcyclopropane, achieving a one-step, highly efficient synthesis of β-amino ketone compounds. The electro-photocatalytic synthesis method of this invention features mild reaction conditions, requires no stoichiometric chemical oxidants, is simple to operate, and has high synthesis efficiency. Furthermore, the reaction system exhibits good functional group tolerance, compatible with various functional groups, heterocycles, and complex structural substrates, demonstrating promising application prospects and widespread value in organic synthesis, drug synthesis, and medicinal chemistry.

[0007] To achieve these objectives and other advantages according to the present invention, an electro-photocatalytic synthesis method for β-amino ketone compounds is provided, comprising: reacting compound I and compound II of the following formula in an organic solvent in the presence of a catalyst and an electrolyte, through the combined action of electrolysis and light irradiation, to generate β-amino ketone compound III; Wherein, Ar is independently selected from phenyl, substituted phenyl, and R is independently selected from hydrogen, alkyl, phenyl, substituted phenyl; It is independently selected from pyrazole, substituted pyrazole, triazole, benzotriazole, and substituted benzotriazole.

[0008] Preferably, the catalyst is a triaminocyclopropylene onium salt having the following structure: .

[0009] Preferably, the electrolyte is lithium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, or tetrabutylammonium perchlorate.

[0010] Preferably, the anode of the electrolytic cell used in the electrolysis is a carbon felt electrode, the cathode is a platinum electrode, and the constant voltage of the electrolysis is 2.0 V.

[0011] Preferably, the illumination condition is visible light illumination, specifically 23 W energy-saving lamp illumination.

[0012] Preferably, the molar ratio of compound II to compound I is 1 to 6.

[0013] Preferably, the organic solvent is acetonitrile, acetone, N,N-dimethylformamide, ethyl acetate, methanol, dichloromethane, dichloroethane, or toluene.

[0014] Preferably, the molar amount of the catalyst triaminocyclopropeneonium is 8% of the molar amount of compound I.

[0015] Preferably, in which, Independently selected from pyrazole, 4-bromo-1H-pyrazole, 4-chloro-1H-pyrazole, 4-iodo-1H-pyrazole, 4-bromo-3-methyl-1H-pyrazole, methyl 4-chloro-1H-pyrazole-3-carboxylate, 1-(1H-pyrazole-4-yl)acetone, methyl 1H-pyrazole-4-carboxylate, ethyl 1H-pyrazole-4-carboxylate, 1H-pyrazole-4-carboxylate, 1H-pyrazole-4-carboxaldehyde, 1H-pyrazole-4- Formonitrile, 1H-1,2,3-triazole, 1H-benzo[d][1,2,3]triazole, 1H-benzo[d][1,2,3]triazole-5-carboxylonitrile, (S)-pyrrolidine-1,2-dicarboxylic acid-1-tert-butyl ester-2-((1H-pyrazole-4-yl)methyl) ester, (S)-2-(6-methoxynaphthyl-2-yl)propionic acid (1H-pyrazole-4-yl)methyl ester.

[0016] Preferably, the substituents in the substituted phenyl group of Ar are halogen, methyl, or methoxy; and the substituents in the substituted phenyl group of R are halogen, methyl, or methoxy.

[0017] The present invention has at least the following beneficial effects: 1. The electro-photocatalytic synthesis method of β-amino ketone compounds of the present invention provides a simple and efficient route for the regioselective conversion of arylcyclopropane to β-amino ketone.

[0018] 2. The electro-photocatalytic synthesis method of β-amino ketone compounds of the present invention achieves dual nucleophilic addition of arylcyclopropane by coupling electrochemical and photochemical activation, while ensuring 100% molecular utilization and eliminating the need for stoichiometric chemical oxidants.

[0019] 3. The mild reaction conditions of the electro-photocatalytic synthesis method for β-aminoketone compounds of the present invention enable the system to be compatible with a variety of functional groups, heterocycles and complex substrates, highlighting its potential application value in synthetic chemistry and medicinal chemistry.

[0020] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0021] Figure 1 The 1H NMR spectrum of compound 1 prepared by the synthesis method in Example 1 of this invention; Figure 2 The 1H NMR spectrum of compound 2 prepared by the synthesis method in Example 2 of this invention; Figure 3 The 1H NMR spectrum of compound 3 prepared by the synthesis method in Example 3 of this invention; Figure 4 The 1H NMR spectrum of compound 4 prepared by the synthesis method in Example 4 of this invention; Figure 5 The 1H NMR spectrum of compound 5 prepared by the synthesis method in Example 5 of this invention; Figure 6 The 1H NMR spectrum of compound 6 prepared by the synthesis method in Example 6 of this invention; Figure 7 The 1H NMR spectrum of compound 7 prepared by the synthesis method in Example 7 of this invention; Figure 8 The 1H NMR spectrum of compound 8 prepared by the synthesis method in Example 8 of this invention. Detailed Implementation

[0022] The present invention will now be described in further detail so that those skilled in the art can implement it based on the description.

[0023] It should be noted that, unless otherwise specified, the experimental methods described in the following implementation plan are all conventional methods, and the reagents and materials described are all commercially available unless otherwise specified.

[0024] The electrolytic cell used in this embodiment is a commercially available H-type electrolytic cell, specifically an H-type sand-core ordinary electrolytic cell from Tianjin Lanlike Chemical Electronics High-Tech Co., Ltd. The electrolytic cell selected in this embodiment has a volume of 10 mL, with the anode and cathode chambers separated by a glass frit core. The electrode used in the anode chamber is a carbon felt electrode, and the electrode used in the cathode chamber is a platinum electrode. The electrolyte used in this embodiment is an acetonitrile solution of lithium perchlorate.

[0025] Example 1 1,3-Diphenyl-3-(1H-pyrazol-1-yl)prop-1-one (compound 1) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), pyrazole (40.9 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell, while lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 1, a pale yellow solid (85.0 mg, yield: 77%), which is a β-amino ketone compound.

[0026] Among them, the triaminocyclopropene onium salt has the following structure: In subsequent examples, the catalyst is a triaminocyclopropylene onium salt with the same structure.

[0027] 1 H NMR (400 MHz, CDCl3) δ 8.0-7.9 (m, 2H), 7.6-7.5 (m, 1H), 7.5 (dd, J= 5.4, 2.1 Hz, 2H), 7.5-7.4 (m, 2H), 7.4-7.3 (m, 5H), 6.2 (t, J = 2.1 Hz, 1H), 6.1 (dd, J = 8.4, 5.2 Hz, 1H), 4.5 (dd, J = 17.7, 8.4 Hz, 1H), 3.6 (dd, J= 17.7, 5.2 Hz, 1H). 13 HRMS (ESI)exact mass: calculated for (M+H) + : 277.1335; found: 277.1336. The existing synthetic methods for compound 1 mainly include three types: (1) preparation via Michael reaction using chalcone and pyrazole as raw materials, with alkali and high temperature (110℃) as reaction conditions (CN 104030984 B); (2) preparation via oxidative addition reaction using 1,2-diphenylcyclopropane and pyrazole as raw materials, with titanium dioxide and light as reaction conditions (CN 104030984 B); J. Org. Chem ., 2022,87, 13627-13642); (3) using 1,3-diphenyl-2-propyn-1-ol and pyrazole as raw materials, the preparation was carried out under the action of alkali and high temperature ( Org. Biomol. Chem. (2012, 10, 3538-3555). The method used in this embodiment is more environmentally friendly and milder than existing synthesis methods, requiring no alkali, metal catalysts, high temperatures, or other reaction conditions.

[0028] Example 2 3-(4-bromo-1H-pyrazol-1-yl)-1,3-diphenylprop-1-one (compound 2) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 4-bromopyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 2, a pale yellow solid (101.9 mg, yield: 72%), which is a β-amino ketone compound.

[0029] 1H NMR (400 MHz, CDCl3) δ 8.00-7.95 (m, 2H), 7.59-7.55 (m, 1H), 7.50(s, 1H), 7.48-7.43 (m, 3H), 7.37-7.29 (m, 6H), 6.05 (dd, J = 8.8, 5.0 Hz, 1H), 4.49 (dd, J = 17.8, 8.8 Hz, 1H), 3.57 (dd, J = 17.8, 4.9 Hz, 1H). 13 HRMS (ESI) exact mass:calculated for (M+H) + :355.0441; found: 355.0439. The existing synthetic method for compound 2 involves an oxidative addition reaction using 1,2-diphenylcyclopropane and pyrazole as starting materials, with titanium dioxide and light irradiation as reaction conditions. J. Org. Chem. (2022, 87, 13627-13642). The method used in this embodiment has a higher yield and greener reaction conditions than the reported method, and does not require the use of stoichiometric titanium dioxide as a catalyst.

[0030] Example 3 3-(4-chloro-1H-pyrazol-1-yl)-1,3-diphenylprop-1-one (compound 3) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 4-chloro-1H-pyrazole (61.5 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 3, a pale yellow solid (52.1 mg, yield: 42%), which is a β-amino ketone compound.

[0031] 1 H NMR (400 MHz, CDCl3) δ 8.00-7.95 (m, 2H), 7.61-7.54 (m, 1H), 7.47(t, J = 3.9 Hz, 3H), 7.41 (s, 1H), 7.36-7.29 (m, 5H), 6.03 (dd, J = 8.8, 4.9 Hz, 1H), 4.48 (dd, J = 17.7, 8.8 Hz, 1H), 3.56 (dd, J = 17.7, 4.9 Hz, 1H). 13 C NMR (101MHz, CDCl3) δ 196.3, 140.0, 137.7, 133.6, 129.0, 128.7, 128.4, 128.2, 127.9,126.7, 110.1,61.4, 43.7. HRMS (ESI) exact mass: calculated for (M+H) + :311.0946; found: 311.0945. Example 4 3-(4-iodo-1H-pyrazol-1-yl)-1,3-diphenylprop-1-one (compound 4) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 4-iodo-1H-pyrazole (116.4 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 4, a pale yellow solid (101.3 mg, yield: 63%), which is a β-amino ketone compound.

[0032] 1 H NMR (400 MHz, CDCl3) δ 8.00-7.94 (m, 2H), 7.60-7.54 (m, 1H), 7.52(s, 1H), 7.49 (s, 1H), 7.45 (t, J = 7.7 Hz, 2H), 7.37-7.30 (m, 5H), 6.09 (dd, J =8.7, 4.9 Hz, 1H), 4.48 (dd, J = 17.7, 8.7 Hz, 1H), 3.58 (dd, J = 17.8, 5.0 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 196.3, 144.4, 140.1, 136.5, 134.3, 133.6,129.0, 128.8, 128.4, 128.3, 126.8, 61.4, 43.9. HRMS (ESI) exact mass:calculated for (M+H) + :403.0302; found: 403.0303. Example 5 3-(4-bromo-3-methyl-1H-pyrazol-1-yl)-1,3-diphenylprop-1-one (compound 5) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 4-bromo-3-methyl-1H-pyrazole (96.6 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 5, a pale yellow solid (60.6 mg, yield: 41%), which is a β-amino ketone compound.

[0033] 1 H NMR (400 MHz, CDCl3) δ 8.01-7.93 (m, 2H), 7.59-7.54 (m, 1H), 7.45(t, J = 7.8 Hz, 2H), 7.39 (s, 1H), 7.36-7.28 (m, 3H), 7.24 (dd, J = 6.6, 1.8 Hz, 2H), 6.03 (dd, J = 9.5, 4.1 Hz, 1H), 4.63 (dd, J = 17.8, 9.5 Hz, 1H), 3.47 (dd, J =17.9, 4.1 Hz, 1H), 2.29 (s, 3H). 13HRMS (ESI) exactmass: calculated for (M+H) + :369.0597; found:369.0598. Example 6 4-Chloro-1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazole-3-carboxylic acid methyl ester (compound 6) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), methyl 4-chloro-1H-pyrazole-3-carboxylate (96.4 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 6, a pale yellow solid (60.5 mg, yield: 41%), which is a β-amino ketone compound.

[0034] 1 H NMR (400 MHz, CDCl3) δ 7.99-7.95 (m, 2H), 7.60-7.55 (m, 1H), 7.53(s, 1H), 7.45 (d, J = 7.6 Hz, 2H), 7.36-7.32 (m, 5H), 6.08 (dd, J = 8.2, 5.4 Hz, 1H), 4.48 (dd, J= 17.9, 8.2 Hz, 1H), 3.90 (s, 3H), 3.68 (dd, J = 17.9, 5.4 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 196.1, 161.6, 138.9, 136.3, 133.8, 130.4,129.2, 128.8, 128.8, 128.4, 128.3, 127.0, 127.0, 62.7, 52.1, 43.7.HRMS (ESI)exact mass: calculated for (M+H) + :369.1000; found: 369.1002. Example 7 3-(4-acetyl-1H-pyrazole-1-yl)-1,3-diphenylprop-1-one (compound 7) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 1-(1H-pyrazol-4-yl)acetone (66.1 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 7, a pale yellow solid (80.2 mg, yield: 63%), which is a β-amino ketone compound.

[0035] 1 H NMR (400 MHz, CDCl3) δ 7.99 (s, 1H), 7.98-7.94 (m, 2H), 7.89 (s,1H), 7.62-7.54 (m, 1H), 7.46 (t,J = 7.8 Hz, 2H), 7.36 (d, J = 4.6 Hz, 4H), 7.34-7.31 (m, 1H), 6.09 (dd, J = 9.0, 4.6 Hz, 1H), 4.51 (dd, J = 17.9, 9.0 Hz, 1H), 3.60 (dd, J = 17.8, 4.7 Hz, 1H), 2.38 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 196.2,192.2, 140.4, 139.5, 136.3, 133.8, 132.6, 129.2, 128.8, 128.7, 128.3, 126.9,124.2, 61.7, 43.8, 28.0. HRMS (ESI)exact mass: calculated for (M+H) + :319.1441; found: 319.1444. Example 8 1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazole-4-carboxylic acid methyl ester (compound 8) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), methyl 1H-pyrazole-4-carboxylate (75.7 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 8, a pale yellow solid (81.5 mg, yield: 61%), which is a β-amino ketone compound.

[0036] 1 H NMR (400 MHz, CDCl3) δ 7.99 (s, 1H), 7.98-7.94 (m, 2H), 7.89 (s,1H), 7.61-7.52 (m, 1H), 7.45 (t, J = 7.7 Hz, 2H), 7.35 (d, J = 4.4 Hz, 4H), 7.33-7.30 (m, 1H), 6.09 (dd, J = 8.7, 4.9 Hz, 1H), 4.48 (dd, J = 17.8, 8.8 Hz, 1H), 3.78 (s, 3H), 3.62 (dd, J = 17.8, 4.9 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 196.2,163.5, 141.1, 139.6, 136.4, 133.7, 133.4, 129.1, 128.8, 128.6, 128.3, 126.9,114.9, 61.7, 51.4, 43.8. HRMS (ESI)exact mass: calculated for (M+H) + :335.1390; found: 335.1391. Example 9 1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazole-4-carboxylic acid ethyl ester (compound 9) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), ethyl 1H-pyrazole-4-carboxylate (84.1 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 9, a pale yellow solid (51.5 mg, yield: 37%), which is a β-amino ketone compound.

[0037] 1 H NMR (400 MHz, CDCl3) δ 8.0 (s, 1H), 8.0-7.9 (m, 2H), 7.9 (s, 1H),7.6-7.5 (m, 1H), 7.5 (t, J = 7.7 Hz, 2H), 7.4-7.3 (m, 5H), 6.1 (dd, J = 8.8, 4.9Hz, 1H), 4.5 (dd, J = 17.8, 8.8 Hz, 1H), 4.2 (q, J = 7.1 Hz, 2H), 3.6 (dd, J =17.8, 4.9 Hz, 1H), 1.3 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 196.2,163.1, 141.1, 139.7, 136.4, 133.7, 133.3, 129.1, 128.8, 128.5, 128.3,126.9,115.2, 104.0, 61.6, 60.2, 43.8, 14.5. HRMS (ESI) exact mass: calculated for (M+H) +:349.1547; found: 349.1545. Example 10 1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazole-4-carboxaldehyde (compound 10) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 1H-pyrazole-4-carboxaldehyde (57.7 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 10, a pale yellow solid (60.8 mg, yield: 50%), which is a β-amino ketone compound.

[0038] 1 H NMR (400 MHz, CDCl3) δ 9.81 (s, 1H), 8.03 (s, 1H), 7.98-7.94 (m,3H), 7.58 (t, J = 7.4 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 3.9 Hz, 5H), 6.12 (dd, J = 8.9, 4.7 Hz, 1H), 4.52 (dd, J = 17.9, 9.0 Hz, 1H), 3.62 (dd, J =17.9, 4.7 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 196.0, 184.0, 140.4, 139.1,136.2, 133.7, 133.6, 129.1, 128.8, 128.7, 128.2,126.9, 124.2, 61.8, 43.7.HRMS (ESI) exact mass: calculated for (M+H) + :305.1285; found: 305.1285. Example 11 1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazole-4-carboxynitrile (compound 11) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 1H-pyrazole-4-carboxynitrile (55.9 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 11, a pale yellow solid (72.3 mg, yield: 60%), which is a β-amino ketone compound.

[0039] 1 H NMR (400 MHz, CDCl3) δ 7.98-7.93 (m, 2H), 7.92 (s, 1H), 7.76 (s,1H), 7.59 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.7 Hz, 2H), 7.40-7.34 (m, 5H), 6.09(dd, J= 9.2, 4.4 Hz, 1H), 4.51 (dd, J = 17.9, 9.2 Hz, 1H), 3.58 (dd, J = 17.9, 4.5Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 195.9, 142.2, 138.8, 136.1, 135.0, 133.8,129.2, 128.8, 128.8, 128.2, 126.8, 113.4, 92.4,61.9, 43.7. HRMS (ESI) exactmass: calculated for (M+H) + :302.1288; found: 302.1284. Example 12 1,3-Diphenyl-3-(1H-1,2,3-triazol-1-yl)prop-1-one (compound 12) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 1H-1,2,3-triazole (36.7 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 12, a pale yellow solid (68.7 mg, yield: 62%), which is a β-amino ketone compound.

[0040] 1 H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 8.4, 1.3 Hz, 2H), 7.68 (d, J= 1.0Hz, 1H), 7.62-7.54 (m, 2H), 7.45 (t, J = 7.7 Hz, 2H), 7.38-7.32 (m, 5H), 6.31(dd, J = 8.6, 5.1 Hz, 1H), 4.66 (dd, J = 17.9, 8.6 Hz, 1H), 3.74 (dd, J = 17.9, 5.1Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 196.0, 139.2, 136.3, 134.0, 133.8, 129.3,128.9, 128.8, 128.3, 127.0, 124.4, 60.5, 44.4. HRMS (ESI) exact mass:calculated for(M+H) + :278.1288; found: 278.1289. Example 13 3-(1H-benzo[d][1,2,3]triazol-1-yl)-1,3-diphenylprop-1-one (compound 13) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 1H-benzo[d][1,2,3]triazole (71.5 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 13, a pale yellow solid (54.9 mg, yield: 42%), which is a β-amino ketone compound.

[0041] 1 H NMR (400 MHz, CDCl3) δ 8.01 (dd, J = 12.9, 7.6 Hz, 3H), 7.58 (t, J =7.6 Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.49 – 7.43 (m, 3H), 7.40 (d, J = 7.9 Hz,2H), 7.36 – 7.28 (m, 4H), 6.58 (dd, J = 8.6, 4.8 Hz, 1H), 4.86 (dd, J = 17.9, 8.8Hz, 1H), 3.89 (dd, J = 17.9, 4.9 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 196.0,146.2, 139.2, 136.4, 133.8, 133.2, 129.2, 128.9, 128.7, 128.4, 127.6, 126.9,124.3, 120.0, 110.1, 58.6, 44.6. HRMS(ESI) exact mass: calculated for (M+H) + :328.1444; found: 328.1444. Example 14 1-(3-oxo-1,3-diphenylpropyl)-1H-benzo[d][1,2,3]triazole-5-carboxynitrile (compound 14) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), 1H-benzo[d][1,2,3]triazole-5-carboxynitrile (86.5 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 14, a pale yellow solid (77.5 mg, yield: 55%), which is a β-amino ketone compound.

[0042] 1 H NMR (400 MHz, CDCl3) δ 8.13 (dd, J = 8.6, 0.9 Hz, 1H), 8.01-7.95 (m,2H), 7.93 (s, 1H), 7.63-7.53 (m, 2H), 7.47 (t, J = 7.8 Hz, 2H), 7.42-7.34 (m,5H), 6.55 (dd, J = 9.5, 4.2 Hz, 1H), 4.92 (dd, J = 18.1, 9.5 Hz, 1H), 3.84 (dd, J =18.1, 4.2 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 195.7, 147.5, 138.2, 136.1,134.0, 132.6, 129.6, 129.2, 128.9, 128.4, 126.8,126.6, 121.5, 118.6, 116.1,111.1, 59.3, 44.5. HRMS (ESI) exact mass: calculated for (M+H) +: 353.1397; found: 353.1401. Example 15 (2S)-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-[(1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazole-4-yl)methyl] ester (compound 15), which has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), (S)-pyrrolidine-1,2-dicarboxylic acid-1-tert-butyl ester-2-((1H-pyrazol-4-yl)methyl) ester (177.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. In the cathode chamber, lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, and extracted with ethyl acetate (3 × 20 mL). The organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 15, a pale yellow solid (82.6 mg, yield: 41%), which is a β-aminoketone compound.

[0043] 1 H NMR (400 MHz, CDCl3) δ 8.17 (d, J = 9.1 Hz, 1H), 7.96 (d, J = 8.3 Hz, 2H), 7.68 (d, J = 8.1 Hz, 1H), 7.58 (d, J = 5.5 Hz, 1H), 7.49-7.43 (m, 4H), 7.37(d, J = 6.0 Hz, 2H), 7.31 (d, J = 5.8 Hz, 1H), 5.51 (d, J = 27.3 Hz, 1H), 5.35 (t, J= 6.1 Hz, 1H), 4.37 (d, J = 14.5 Hz, 2H), 3.38 (d, J = 6.0 Hz, 2H), 1.96 (m, 4H), 1.28 (d, J = 4.0 Hz, 9H), 1.26 (s, 2H). 13 C NMR (101 MHz, CDCl3) δ 200.3, 171.5,154.5, 153.8, 144.1, 143.1, 136.7, 133.8, 129.1, 128.9, 128.7,128.3, 127.8,126.7, 125.9, 80.1, 70.2, 58.2, 55.2, 47.5, 46.8, 31.5, 30.6, 28.6, 28.3,27.7, 23.8. HRMS (ESI) exact mass: calculated for (M+H) + : 504.2493; found: 504.2496. Example 16 (1-(3-oxo-1,3-diphenylpropyl)-1H-pyrazol-4-yl)methyl(2S)-2-(6-methoxynaphthyl-2-yl)propionate (compound 16) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-diphenylcyclopropane (77.6 mg, 0.4 mmol), (S)-2-(6-methoxynaphthyl-2-yl)propionic acid (1H-pyrazol-4-yl)methyl ester (186.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. In the cathode chamber, lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, and extracted with ethyl acetate (3 × 20 mL). The organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 16, a pale yellow solid (91.2 mg, yield: 44%), which is a β-aminoketone compound.

[0044] 1 H NMR (400 MHz, CDCl3) δ 8.07-7.99 (m, 1H), 7.97 – 7.94 (m, 2H), 7.66-7.56 (m, 6H), 7.45-7.40 (m, 4H), 7.29 (d, J = 1.7 Hz, 4H), 7.08 (d, J = 5.9Hz, 1H), 6.03-5.97 (m, 1H), 5.02 – 4.92 (m, 2H), 4.42 (ddd, J = 17.7, 8.3, 1.7Hz, 1H), 3.90 (m, 3H), 3.84-3.80 (m, 1H), 3.61 (dt, J = 17.8, 5.5 Hz, 1H), 1.53(d, J = 3.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 196.5, 174.6, 157.7, 145.0,139.6, 135.7, 133.6, 132.9, 130.7, 130.3, 129.4, 129.1,129.0, 129.0, 128.8,128.7, 128.6, 128.3, 128.3, 127.2, 126.9, 126.3, 126.1, 122.3, 119.1, 116.6,105.7, 61.2, 57.8, 55.4, 45.5, 44.2, 18.7.HRMS (ESI) exactmass: calculatedfor (M+H) + :519.2278; found: 519.2280. Example 17 3-(4-bromo-1H-pyrazol-1-yl)-1-phenylprop-1-one (compound 17) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropenemonium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), cyclopropylbenzene (47.2 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 17, a pale yellow solid (35.7 mg, yield: 32%), which is a β-amino ketone compound.

[0045] 1 H NMR (400 MHz, CDCl3) δ 7.93 (s, 2H), 7.57 (d, J= 12.0 Hz, 2H), 7.51-7.42 (m, 3H), 4.57 (t, J = 6.3 Hz, 2H), 3.57 (t, J = 6.4 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 197.1, 140.2, 136.3, 133.8, 130.6, 128.9, 128.2, 92.9, 47.3, 38.6.HRMS (ESI) exact mass: calculated for (M+H) + :279.0128; found: 279.0130. Example 18 3-(4-bromo-1H-pyrazol-1-yl)-1-(4-bromophenyl)prop-1-one (compound 18) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropenemonium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1-bromo-4-cyclopropylbenzene (78.8 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 18, a pale yellow solid (54.4 mg, yield: 38%), which is a β-amino ketone compound.

[0046] 1 H NMR (400 MHz, CDCl3) δ 7.83-7.77 (m, 2H), 7.64-7.58 (m, 2H), 7.53(s, 1H), 7.44 (s, 1H), 4.55 (t, J= 6.3 Hz, 2H), 3.53 (t, J = 6.3 Hz, 2H). 13 C NMR(101 MHz, CDCl3) δ 196.2, 140.3, 135.0, 132.2, 130.6, 129.7, 129.1, 92.9,47.2, 38.5. HRMS (ESI)exact mass: calculated for (M+H) + :356.9233; found:356.9230. Example 19 3-(4-bromo-1H-pyrazol-1-yl)-1-phenylbut-1-one (compound 19) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropenemonium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), (2-methylcyclopropyl)benzene (53.3 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to obtain compound 19, a pale yellow solid (70.4 mg, yield: 60%), which is a β-amino ketone compound.

[0047] 1 H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 7.0 Hz, 2H), 7.66-7.52 (m, 2H),7.49 – 7.37 (m, 3H), 5.03 (h, J = 6.8 Hz, 1H), 3.78 (dd, J= 17.5, 7.0 Hz, 1H), 3.29 (dd, J = 17.6, 5.9 Hz, 1H), 1.60 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3)δ 197.1, 140.0, 136.6, 133.7, 129.2, 128.8, 128.2, 92.5, 54.3, 45.0, 21.3.HRMS (ESI)exact mass: calculated for (M+H) + :293.0284; found: 293.0286. Example 20 3-(4-bromo-1H-pyrazol-1-yl)-3-methyl-1-phenylbut-1-one (compound 20) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropenemonium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), (2,2-dimethylcyclopropyl)benzene (58.6 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 20, a pale yellow solid (30.7 mg, yield: 25%), which is a β-amino ketone compound.

[0048] 1 H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 1.2 Hz, 1H), 7.82 (d, J= 1.5 Hz,1H), 7.54-7.51 (m, 2H), 7.44-7.39 (m, 3H), 3.56 (s, 2H), 1.76 (s, 6H). 13 C NMR(101 MHz, CDCl3) δ 197.4, 139.6, 137.4, 133.3, 128.6, 128.1, 127.1, 88.9,59.2, 48.7, 27.9. HRMS(ESI) exact mass: calculated for (M+H) + :307.0441;found: 307.0444. Example 21 3-(4-bromo-1H-pyrazol-1-yl)-1-(4-bromophenyl)-3-methylbut-1-one (compound 21) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1-bromo-4-(2,2-dimethylcyclopropyl)benzene (90.1 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 21, a pale yellow solid (92.7 mg, yield: 50%), which is a β-amino ketone compound.

[0049] 1 H NMR (400 MHz, CDCl3) δ 7.72-7.65 (m, 2H), 7.59-7.52 (m, 2H), 7.52(s, 1H), 7.41 (s, 1H), 3.51 (s, 2H), 1.73 (s, 6H). 13C NMR (101 MHz, CDCl3) δ196.4, 139.6, 136.1, 131.9, 129.7, 128.6, 127.0, 92.4, 60.6, 48.6, 27.9. HRMS(ESI)exact mass: calculated for (M+H) + :384.9546; found: 384.9541. Example 22 3-(4-bromo-1H-pyrazol-1-yl)-3-methyl-1-(p-tolyl)but-1-one (compound 22) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1-(2,2-dimethylcyclopropyl)-4-toluene (64.1 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 22, a pale yellow solid (71.9 mg, yield: 56%), which is a β-amino ketone compound.

[0050] 1 H NMR (400 MHz, CDCl3) δ 7.75-7.69 (m, 2H), 7.53 (s, 1H), 7.43 (s,1H), 7.22-7.16 (m, 2H), 3.52 (s, 2H), 2.38 (s, 3H), 1.75 (s, 6H). 13C NMR (101MHz, CDCl3) δ 197.0, 144.2, 139.5, 135.0, 129.3, 128.3, 127.1, 92.3, 60.7,48.6, 27.8,21.8. HRMS (ESI) exact mass: calculated for (M+H) + :321.0597;found: 321.0595. Example 23 3-(4-bromo-1H-pyrazol-1-yl)-1-(4-methoxyphenyl)-3-methylbut-1-one (compound 23) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1-(2,2-dimethylcyclopropyl)-4-methoxybenzene (70.5 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 23, a pale yellow solid (52.6 mg, yield: 39%), which is a β-amino ketone compound.

[0051] 1 H NMR (400 MHz, CDCl3) δ 7.88-7.76 (m, 2H), 7.53 (s, 1H), 7.45 (s,1H), 6.93-6.82 (m, 2H), 3.85 (s, 3H), 3.50 (s, 2H), 1.75 (s, 6H). 13C NMR (101MHz, CDCl3) δ 195.9, 163.7, 139.4, 130.6, 130.5, 127.2, 113.8, 92.3, 60.9,55.6, 48.4,27.9. HRMS (ESI) exact mass: calculated for (M+H) + :337.0546;found: 337.0549. Example 24 3-(4-bromo-1H-pyrazol-1-yl)-1,3-di(4-bromophenyl)prop-1-one (compound 24) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropene onium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1,2-bis(4-bromophenyl)cyclopropane (140.8 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the constant voltage of the electrolysis conditions was set to 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate (volume ratio) = 2:1) to give compound 24, a pale yellow solid (108.8 mg, yield: 53%), which is a β-amino ketone compound.

[0052] 1 H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 8.5 Hz, 2H), 7.49-7.43 (m, 4H), 7.23-7.16 (m, 2H), 5.97 (dd, J = 8.6, 5.1 Hz, 1H), 4.40(dd, J= 17.7, 8.6 Hz, 1H), 3.48 (dd, J = 17.7, 5.1 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 195.2, 144.1, 140.2, 138.9, 135.1, 132.2, 132.2, 130.1, 129.8,129.1, 128.6, 122.6, 93.8, 60.9, 43.6. HRMS (ESI) exactmass: calculated for (M+H) + :510.8651; found: 510.8655. Example 25 3-(4-bromo-1H-pyrazol-1-yl)-1-(4-chlorophenyl)-3-(p-tolyl)prop-1-one (compound 25) has the following structural formula: Specific synthesis methods include: Under argon protection, triaminocyclopropenemonium salt (15.2 mg, 0.032 mmol), lithium perchlorate (85.1 mg, 0.8 mmol), 1-chloro-4-(2-p-tolylcyclopropyl)benzene (97.1 mg, 0.4 mmol), 4-bromo-1H-pyrazole (88.2 mg, 0.6 mmol), and acetonitrile (4.0 mL) were added to the anode chamber of the electrolytic cell. Lithium perchlorate (85.1 mg, 0.8 mmol), trifluoroacetic acid (100 μL), and acetonitrile (4.0 mL) were added to the cathode chamber. During the reaction, two 23W energy-saving light bulbs were used for irradiation, and the electrolysis conditions were maintained at a constant voltage of 2.0 V for 12 hours. After the reaction was complete, the reaction mixture was poured into a saturated sodium bicarbonate solution (20 mL), the aqueous layer was separated, extracted with ethyl acetate (3 × 20 mL), and the organic layers were combined. The organic layer was washed with saturated brine and dried with anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 2:1) to give compound 25, a pale yellow solid (82.3 mg, yield: 51%), which is a β-amino ketone compound.

[0053] 1 H NMR (400 MHz, CDCl3) δ 7.92-7.88 (m, 2H), 7.45 (s, 1H), 7.43 (d, J =2.0 Hz, 1H), 7.42 (d, J= 1.9 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H), 7.15 (d, J = 8.1Hz, 2H), 5.98 (dd, J = 8.7, 5.0 Hz, 1H), 4.42 (dd, J = 17.6, 8.7 Hz, 1H), 3.49(dd, J = 17.6, 5.0 Hz, 1H), 2.33 (s, 3H). 13 HRMS (ESI) exact mass: calculated for (M+H) + :403.0207;found:403.0209. Although the technical solutions of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and embodiments shown and described herein.

Claims

1. A method for the electro-photocatalytic synthesis of β-aminoketone compounds, characterized in that, include: In an organic solvent, compounds I and II of the following formula react to generate β-amino ketone compound III in the presence of a catalyst and an electrolyte through the combined action of electrolysis and light irradiation. Wherein, Ar is independently selected from phenyl, substituted phenyl, and R is independently selected from hydrogen, alkyl, phenyl, substituted phenyl; It is independently selected from pyrazole, substituted pyrazole, triazole, benzotriazole, and substituted benzotriazole.

2. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, The catalyst is a triaminocyclopropylene onium salt, which has the following structure: 。 3. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, The electrolyte is lithium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, or tetrabutylammonium perchlorate.

4. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, The anode in the electrolytic cell used in the electrolysis is a carbon felt electrode, and the cathode is a platinum electrode. The constant voltage for electrolysis is 2.0 V.

5. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, The lighting conditions are visible light irradiation, specifically irradiation by a 23W energy-saving lamp.

6. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, The molar ratio of compound II to compound I is 1 to 6.

7. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, The organic solvent is acetonitrile, acetone, N,N-dimethylformamide, ethyl acetate, methanol, dichloromethane, dichloroethane, or toluene.

8. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 2, characterized in that, The molar amount of the catalyst triaminocyclopropeneonium was 8% of the molar amount of compound I.

9. The electro-photocatalytic synthesis method for β-aminoketone compounds as described in claim 1, characterized in that, Independently selected from pyrazole, 4-bromo-1H-pyrazole, 4-chloro-1H-pyrazole, 4-iodo-1H-pyrazole, 4-bromo-3-methyl-1H-pyrazole, methyl 4-chloro-1H-pyrazole-3-carboxylate, 1-(1H-pyrazole-4-yl)acetone, methyl 1H-pyrazole-4-carboxylate, ethyl 1H-pyrazole-4-carboxylate, 1H-pyrazole-4-carboxaldehyde, 1H-pyrazole-4-carboxylate, etc. -Formonitrile, 1H-1,2,3-triazole, 1H-benzo[d][1,2,3]triazole, 1H-benzo[d][1,2,3]triazole-5-formonitrile, (S)-pyrrolidine-1,2-dicarboxylic acid-1-tert-butyl ester 2-((1H-pyrazole-4-yl)methyl) ester, (S)-2-(6-methoxynaphthyl-2-yl)propionic acid (1H-pyrazole-4-yl)methyl ester.

10. The electro-photocatalytic synthesis method of β-aminoketone compounds as described in claim 1, characterized in that, The substituents in the Ar-substituted phenyl group are halogen, methyl, or methoxy; the substituents in the R-substituted phenyl group are halogen, methyl, or methoxy.

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