Method for constructing C-N bond or C-C bond through insertion reaction of oxygen-sulfur ylide and aromatic amine

Abstract

The invention relates to a method for constructing a C-N bond or a C-C bond through an insertion reaction of oxygen-sulfur ylide and aromatic amine. According to the method, tris (pentafluorophenyl) borane is taken as a catalyst, oxygen-sulfur ylide and aromatic amine are taken as raw materials, and N-H or C-H insertion reaction is carried out under different temperatures and solvents. According to the method, the defect that a metal catalyst or an oxidizing agent is used traditionally is overcome, and on the basis of the method, various alpha-amino-acid ester derivatives or diaryl acetate derivatives can be obtained by using different aromatic amines and oxygen-sulfur ylide as substrates. According to the method, the raw materials are easy to obtain, the operation is simple, the use of a catalyst and an oxidizing agent is avoided, and the method is a mild, effective, feasible and environment-friendly method for preparing the alpha-amino-acid ester and the diaryl acetate and has important application value.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compound synthesis and application, and relates to a NH or CH insertion reaction of an oxysulfur ylide with an aromatic amine catalyzed by tris(pentafluorophenyl)borane, thereby constructing α -Green synthesis method of amino acid ester compounds and diaryl acetate compounds. Background Art

[0002] α -Amino acid esters are α -Amino acid derivatives are important subunits widely present in biologically active molecules including drugs. For example, enniatin can strongly inhibit Pdr5p, and has a wide range of antibacterial effects. β -lactam antibiotics and methylphenidate for the treatment of attention deficit hyperactivity disorder contain α -Amino acid ester structure 1-3 Diarylacetates are widely present in a large number of natural products and pharmaceuticals, as well as building blocks of complex molecules. 4 In order to synthesize α -Amino acid esters and diaryl acetates, many methods have been developed 5-10 Among the various methods, transition metal-catalyzed α- The NH insertion reaction of aromatic diazo esters and Friedel-Craft type arylation reactions with arenes offer a promising route in terms of efficiency and practicality. 11-15 However, in the above methods, the use of transition metals and the instability of raw materials still need to be solved. Tri(pentafluorophenyl)borane (B(C6F5)3) is an effective metal-free catalyst with good stability. It was first proposed and prepared by Stone, Massey and Park in 1963. 16 B(C6F5)3 is often used as an activator in homogeneous Ziegler-Natta chemistry. 17 In recent decades, many studies have shown that B(C6F5)3 can catalyze the formation of CC bonds / C-heteroatom bonds. 18-19 It is noteworthy that B(C6F5)3 is a potential candidate to replace transition metal-catalyzed activation of diazo compounds. 20 Since their discovery, oxysulfur ylides have been considered as important synthetic precursors and potential safe alternatives to diazo compounds in metal carbene reactions. 21 . Summary of the invention

[0003] In view of various problems existing in the existing methods for constructing CN bonds and CC bonds, the present invention realizes a method for synthesizing α-amino acid ester compounds by NH insertion or synthesizing diarylacetate compounds by CH insertion using oxysulfur ylide compounds and aromatic amine compounds as raw materials and tri(pentafluorophenyl)borane as a catalyst. The purpose of the present invention is to provide a safe, simple, green and controllable method for nitrogen-hydrogen and carbon-hydrogen insertion reactions of sulfur ylides to simultaneously construct CN bonds and CC bonds. Compared with traditional methods, this method has easy-to-obtain raw materials and mild conditions. It is a mild, safe and environmentally friendly alternative method with broad application prospects.

[0004] The chemical reaction formula of the present invention is as follows: , The preparation steps are as follows: (1) Add oxysulfide ylide compounds, aromatic amine compounds, catalysts and solvents in a clean reactor in sequence, place in an oil bath and stir for 24 hours; (2) After the reaction is completed, the solvent is dried under reduced pressure, and the residue is separated and purified by silica gel thin layer chromatography to obtain the product.

[0005] The oxysulfur ylide in step (1): R1 is hydrogen, methyl, halogen; the aromatic amine compound in step (1): R2 is hydrogen, C1~C5 alkyl, methoxy, halogen, trifluoromethyl, R3 is hydrogen, C1~C3 alkyl, methoxy, halogen, hydroxyl, n=0, 1; the reaction concentration of the oxysulfur ylide in step (1) is 0.2 mmol / L, and the molar ratio of the oxysulfur ylide compound: aromatic amine compound: catalyst is 1:1.5:0.1; the catalyst in step (1) is tri(pentafluorophenyl)borane; the solvent of reaction (a) in step (1) is chloroform, and the solvent of reaction (b) is 1,2-dichloroethane; the oil bath temperature of reaction (a) in step (1) is 50°C, and the oil bath temperature of reaction (b) is 80°C. DETAILED DESCRIPTION

[0006] The present invention is further described below in conjunction with specific embodiments, which is helpful for understanding the present invention, but it cannot be used to limit the scope of the present invention, and the scope of the present invention should be based on the scope of the claims.

[0007] Example 1: Synthesis of Compound 1

[0008] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), aniline (27.3 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in a 50 °C oil bath for 24 h.

[0009] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow solid with a melting point of 88.2-89.1°C and a yield of 92%. 1 H NMR (400 MHz, CDCl3)δ 7.53 (d, J = 6.8Hz, 2H), 7.40-7.29 (m, 3H), 7.15 (dd, J = 8.5, 7.3 Hz, 2H), 6.72 (t, J = 7.3Hz, 1H), 6.59 (d, J = 8.0 Hz, 2H), 5.09 (s, 1H), 4.92 (br, 1H), 4.21 (dd, J =29.8, 7.1 Hz, 2H), 1.23 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 171.92,146.10, 137.83, 129.33, 128.91, 128.32, 127.31, 118.15, 113.52, 61.91, 60.91,14.14; HRMS(ESI) m / z: calcd. 16 H 18 NO2 + : 256.1338, measured value: 256.1336.

[0010] Example 2: Synthesis of Compound 2

[0011] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), 4-methylaniline (32.1 mg, 0.30 mmol), tris(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in an oil bath at 50 °C for 24 h.

[0012] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow solid with a melting point of 88.7-89.5°C and a yield of 98%. 1H NMR (400 MHz, CDCl3)δ 7.52 (d, J = 7.0Hz, 2H), 7.39-7.29 (m, 3H), 6.95 (d, J = 8.0 Hz, 2H), 6.51 (d, J = 8.2 Hz, 2H), 5.06 (s, 1H), 4.83 (br, 1H), 4.20 (dd, J = 29.0, 7.1 Hz, 2H), 2.22 (s,3H), 1.23 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 172.07, 143.84,137.98, 129.84, 128.89, 128.27, 127.33, 113.66, 61.84, 61.21, 20.49, 14.16; HRMS (ESI) m / z: calcd. 17 H 20 NO2 + :270.1494, measured value: 270.1493.

[0013] Example 3: Synthesis of Compound 3

[0014] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), 4-methoxyaniline (36.9 mg, 0.30 mmol), tris(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in an oil bath at 50 °C for 24 h.

[0015] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow oily product with a yield of 76%. 1 H NMR (400 MHz, CDCl3)δ 7.51 (d, J = 6.9 Hz, 2H), 7.39-7.28 (m, 3H), 6.74 (d, J = 8.9 Hz, 2H), 6.55 (d, J = 8.9 Hz, 2H), 5.02 (s,1H), 4.70 (br, 1H), 4.19 (dd, J = 27.5, 7.1 Hz, 2H), 3.71 (s, 3H), 1.22 (t, J= 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3)δ 172.14, 152.57, 140.36, 138.01,128.88, 128.27, 127.34, 114.94, 114.86, 61.79, 55.77, 14.14; HRMS (ESI) m / z: calcd. 17 H 20 NO3 + :286.1443, measured value:286.1440.

[0016] Example 4: Synthesis of Compound 4

[0017] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), 4-bromoaniline (51.6 mg, 0.30 mmol), tris(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in an oil bath at 50 °C for 24 h.

[0018] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a light yellow solid with a melting point of 108.6-109.4°C and a yield of 95%. 1 H NMR (400 MHz, CDCl3)δ 7.48 (d, J =6.7 Hz, 2H), 7.40 -7.29 (m, 3H), 7.20 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 8.8Hz, 2H), 5.02 (s, 1H), 4.19 (dd, J = 30.4, 7.1 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ 171.26, 144.68, 136.96, 131.73, 128.68, 128.17,126.93, 114.78, 109.52, 61.76, 60.42, 13.81; HRMS (ESI) m / z: calcd. 16 H 17 BrNO2 + :334.0443, measured value:334.0444.

[0019] Example 5: Synthesis of Compound 5

[0020] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), 2-tert-butylaniline (46.8 μL, 0.30 mmol), tris(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in a 50 ℃ oil bath for 24 h.

[0021] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a light yellow solid with a melting point of 88.8-89.4°C and a yield of 56%. 1 H NMR (400 MHz, CDCl3)δ 7.54 (d, J = 6.9Hz, 2H), 7.36 (t, J = 7.3 Hz, 2H), 7.31 (d, J = 7.1 Hz, 1H), 7.28 (dd, J =7.8, 1.6 Hz, 1H), 7.01-6.92 (m, 1H), 6.67 (td, J = 7.5, 1.3 Hz, 1H), 6.33 (d,J = 6.8 Hz, 1H), 5.52 (d, J = 5.0 Hz, 1H), 5.14 (d, J = 4.2 Hz, 1H), 4.21(dd, J = 22.0, 7.1 Hz, 2H), 1.56 (s, 9H), 1.23 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ 172.18, 143.90, 138.21, 133.62, 128.91, 128.22, 127.33,127.11, 126.43, 117.44, 112.18, 62.05, 61.19, 34.31, 30.03, 14.14; HRMS (ESI) m / z: calcd. 20 H 26 NO2 + :312.1964, measured value: 312.1960.

[0022] Example 6: Synthesis of Compound 6

[0023] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), 4-trifluoromethylaniline (37.7 μL, 0.30 mmol), tris(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in a 50 °C oil bath for 24 h.

[0024] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a white solid with a melting point of 67.9-69.0°C and a yield of 77%. 1 H NMR (400 MHz, CDCl3)δ 7.49 (d, J = 6.6Hz, 2H), 7.40-7.35 (m, 3H), 7.34-7.29 (m, 2H), 6.57 (d, J = 8.4 Hz, 2H), 5.37(br, 1H), 5.09 (s, 1H), 4.21 (dd, J = 31.0, 7.1 Hz, 2H), 1.23 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 171.37, 148.45, 137.02, 129.10, 128.63, 127.23,126.71 (q, J = 3.8 Hz), 124.95 (d, J = 270.6 Hz), 119.69 (d, J = 32.5 Hz),112.75, 62.26, 60.34, 14.11; 19 F NMR (376 MHz, CDCl3)δ -61.16; HRMS (ESI) m / z: calculated value C 17 H 17 F3NO2 + :324.1211, measured value:324.1214.

[0025] Example 7: Synthesis of Compound 7

[0026] In a clean reactor, α-p-methylphenyl-β-ethoxycarbonylsulfur ylide (50.9 mg, 0.20 mmol), aniline (27.3 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and placed in a 50 ℃ oil bath and stirred for 24 h.

[0027] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow solid with a melting point of 64.5-65.5° C. and a yield of 69%. 1 H NMR (400 MHz, CDCl3)δ 7.38 (d, J = 8.1Hz, 2H), 7.19-7.08 (m, 4H), 6.69 (t, J = 7.4 Hz, 1H), 6.56 (d, J = 7.4 Hz, 2H), 5.03 (s, 1H), 4.18 (dd, J = 33.6, 7.1 Hz, 2H), 2.33 (s, 3H), 1.22 (t, J= 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 172.12, 146.18, 138.09, 134.80,129.64, 129.33, 127.22, 118.10, 113.53, 61.85, 60.65, 21.26, 14.17; HRMS (ESI) m / z: calcd. 17 H 20 NO2 + :270.1494, measured value: 270.1493.

[0028] Example 8: Synthesis of Compound 8

[0029] In a clean reactor, α-p-chlorophenyl-β-ethoxycarbonylsulfur ylide (55.0 mg, 0.20 mmol), aniline (27.3 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in a 50 ℃ oil bath for 24 h.

[0030] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a light yellow oily product with a yield of 95%. 1H NMR (400 MHz, CDCl3)δ 7.47 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.6 Hz, 2H), 7.14 (dd, J = 8.6, 7.3 Hz, 2H), 6.73 (t, J = 7.3Hz, 1H), 6.55 (dd, J = 8.7, 1.1 Hz, 2H), 5.05 (s, 1H), 4.21 (dd, J = 25.8,7.1 Hz, 2H), 1.24 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 171.41,145.77, 136.47, 134.13, 129.37, 129.09, 128.67, 118.34, 113.53, 62.15, 60.25,14.13; HRMS(ESI) m / z: calcd. 16 H 17 ClNO2 + :290.0948, measured value: 290.0946.

[0031] Example 9: Synthesis of Compound 9

[0032] In a clean reactor, α-phenyl-β-methoxycarbonylsulfur ylide (45.3 mg, 0.20 mmol), aniline (27.3 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and chloroform (1 ml) were added in sequence and stirred in a 50 °C oil bath for 24 h.

[0033] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow solid with a melting point of 81.4-82.3° C. and a yield of 98%. 1 H NMR (400 MHz, CDCl3) δ 7.57-7.50 (m,2H), 7.43-7.29 (m, 3H), 7.16 (dd, J = 8.6, 7.3 Hz, 2H), 6.74 (t, J = 7.3 Hz,1H), 6.60 (d, J = 7.6 Hz, 2H), 5.12 (s, 1H), 3.75 (s, 3H); 13C NMR (100 MHz,CDCl3)δ 172.43, 146.04, 137.71, 129.34, 128.98, 128.41, 127.35, 118.22,113.51, 60.83, 52.88; HRMS(ESI) m / z: calcd. 15 H 16 NO2 + :242.1181, measured value: 242.1184.

[0034] Example 10: Synthesis of Compound 10

[0035] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), N, N -Dimethylaniline (38.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0036] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a colorless oily liquid with a yield of 85%. 1 H NMR (400 MHz, CDCl3)δ 7.31 (s, 2H), 7.30 (d, J = 2.4Hz, 2H), 7.25-7.22 (m, 1H), 7.18 (d, J = 8.8 Hz, 2H), 6.69 (d, J = 8.8 Hz, 2H), 4.92 (s, 1H), 4.19 (q, J = 7.1 Hz, 2H), 2.92 (s, 6H), 1.25 (t, J = 7.1 Hz, 3H); 13 CNMR (100 MHz, CDCl3)δ 173.18, 149.82, 139.72, 129.40, 128.61, 128.57, 127.05,126.73, 112.74, 61.11, 56.38, 40.71, 14.31; HRMS(ESI)m / z: calcd. 16 H 22 NO2 +:284.1651, measured value: 284.1654.

[0037] Example 11: Synthesis of Compound 11

[0038] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), N,N -Dimethyl-m-methoxyaniline (44.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0039] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow solid with a melting point of 88.3-90.2° C. and a yield of 60%. 1 H NMR (400 MHz, CDCl3) δ 7.31 (s, 2H), 7.30 (s, 2H), 7.26-7.22 (m, 1H), 6.88 (d, J = 8.1 Hz, 1H), 6.27-6.21 (m, 2H), 5.20 (s, 1H), 4.18 (dd, J = 10.5, 7.1 Hz, 2H), 3.81 (s, 3H), 2.92 (s, 6H), 1.23(t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3)δ 173.63, 157.76, 151.28, 138.84,129.57, 129.09, 128.48, 126.94, 116.32, 104.65, 96.10, 60.85, 55.43, 50.40,40.79, 14.36; HRMS(ESI)m / z: calcd. 19 H 24 NO3 + : 314.1756, Measured value: 314.1755.

[0040] Example 12: Synthesis of Compound 12

[0041] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), N,N -Dimethyl-m-bromoaniline (43.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0042] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a colorless oily liquid with a yield of 64%. 1 H NMR (400 MHz, DMSO- d 6) δ 7.37-7.31 (m, 2H), 7.30-7.25(m, 1H), 7.22 (d, J = 6.8 Hz, 2H), 6.95 (d, J = 8.8 Hz, 1H), 6.89 (d, J = 2.7 Hz,1H), 6.69 (dd, J = 8.8, 2.7 Hz, 1H), 5.26 (s, 1H), 4.13 (dd, J = 7.1, 4.1 Hz,2H), 2.87 (s, 6H), 1.16 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, DMSO- d 6)δ 171.69,150.38, 138.02, 129.90, 128.57, 128.54, 127.13, 125.05, 124.57, 115.29,111.70, 60.79, 54.86, 39.82, 13.98; HRMS(ESI)m / z: calculated C 18 H 21 BrNO2 + :362.0756, measured value: 362.0758.

[0043] Example 13: Synthesis of Compound 13

[0044] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), N,N -Dimethyl-m-methylaniline (44.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0045] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a colorless oily liquid with a yield of 74%. 1 H NMR (400 MHz, CDCl3)δ 7.28 (d, J = 7.4 Hz, 2H), 7.23(d, J = 7.6 Hz, 3H), 7.11 (d, J = 9.4 Hz, 1H), 6.58-6.54 (m, 2H), 5.10 (s, 1H), 4.19 (q, J = 7.1 Hz, 2H), 2.91 (s, 6H), 2.25 (s, 3H), 1.24 (t, J = 7.1 Hz, 3H); 13 CNMR (100 MHz, CDCl3)δ 173.37, 149.76, 139.05, 137.10, 128.97, 128.93, 128.49,126.96, 125.36, 114.81, 110.47, 61.08, 53.14, 40.66, 20.47, 14.32; HRMS(ESI)m / z: calcd. 19 H 24 NO2 + : 298.1807, measured value: 298.1806.

[0046] Example 14: Synthesis of Compound 14

[0047] In a clean reactor, α-phenyl-β-ethoxycarbonylsulfur ylide (48.0 mg, 0.20 mmol), N,N -Dimethyl-m-hydroxyaniline (38.0 μL, 0.30 mmol), tris(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0048] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a green oily liquid with a yield of 57%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.34 (s, 1H), 7.33-7.28 (m, 2H), 7.24-7.21 (m, 3H), 6.72 (d, J = 8.5 Hz, 1H), 6.18 (d, J = 2.5 Hz, 1H), 6.13(dd, J = 8.6, 2.6 Hz, 1H), 5.09 (s, 1H), 4.11-4.05 (m, 2H), 2.81 (s, 6H), 1.14(t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, DMSO- d 6)δ 172.75, 155.16, 150.64, 139.18,128.94, 128.64, 128.22, 126.62, 113.97, 103.71, 99.34, 60.19, 49.46, 40.10,14.06; HRMS(ESI)m / z: calculated value C 18 H 22 NO3 + : 300.1600, measured value: 300.1604.

[0049] Example 15: Synthesis of Compound 15

[0050] In a clean reactor, α-p-methylphenyl-β-ethoxycarbonylsulfur ylide (50.9 mg, 0.20 mmol), N,N -Dimethylaniline (38.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0051] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow oily liquid with a yield of 49%. 1 H NMR (400 MHz, CDCl3)δ 7.21 (t, J = 8.7 Hz, 4H), 7.13(d,J = 7.9 Hz, 2H), 6.71 (d, J = 8.8 Hz, 2H), 4.91 (s, 1H), 4.21 (q, J = 7.1 Hz,2H), 2.94 (s, 6H), 2.33 (s, 3H), 1.27 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz,CDCl3)δ 173.33, 149.78, 136.72, 136.62, 129.32, 129.26, 128.45, 126.95,112.73, 61.04, 55.98, 40.70, 21.14, 14.30; HRMS(ESI)m / z: calcd.C 19 H 24 NO2 + :298.1807, measured value: 298.1805.

[0052] Example 16: Synthesis of Compound 16

[0053] In a clean reactor, α-p-chlorophenyl-β-ethoxycarbonylsulfur ylide (54.9 mg, 0.20 mmol), N,N -Dimethylaniline (38.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0054] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a yellow oily liquid with a yield of 79%. 1 H NMR (400 MHz, CDCl3)δ 7.25 (d, J = 2.3 Hz, 4H), 7.14(d, J = 8.8 Hz, 2H), 6.67 (d, J = 8.8 Hz, 2H), 4.87 (s, 1H), 4.18 (q, J = 7.1 Hz,2H), 2.91 (s, 6H), 1.24 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3)δ 172.81,149.89, 138.25, 132.92, 130.00, 129.23, 128.64, 126.08, 112.69, 61.23, 55.65,40.60, 14.26; HRMS(ESI) m / z: calcd. 18 H 21 ClNO2 + : 318.1261, measured value: 318.1263.

[0055] Example 17: Synthesis of Compound 17

[0056] In a clean reactor, α-phenyl-β-methoxycarbonylsulfur ylide (45.3 mg, 0.20 mmol), N,N -Dimethylaniline (38.0 μL, 0.30 mmol), tri(pentafluorophenyl)borane (10.2 mg, 0.02 mmol) and 1,2-dichloroethane (1 ml) were placed in an oil bath at 80 °C and stirred for 24 h.

[0057] After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography to obtain a colorless oily liquid with a yield of 76%. 1 H NMR (400 MHz, CDCl3)δ 7.30 (d, J = 4.3 Hz, 4H), 7.25-7.22 (m, 1H), 7.17 (d, J = 8.8 Hz, 2H), 6.68 (d, J = 8.8 Hz, 2H), 4.94 (s, 1H), 3.72 (s, 3H), 2.91 (s, 6H); 13 C NMR (100 MHz, CDCl3)δ 173.67, 149.87, 139.53,129.54, 129.38, 128.60, 127.12, 126.48, 112.72, 56.26, 52.30, 40.67; HRMS(ESI) m / z: calcd. 17 H 20 NO2 + : 270.1494, Measured value: 270.1490.

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Claims

1. A method for constructing a CN bond or a CC bond by an insertion reaction of an oxygen-sulfur ylide with an aromatic amine, characterized in that Using oxysulfuryl ylide and aromatic amine as starting materials, chloroform or 1,2-dichloroethane as solvent, under the action of non-metallic catalyst tri(pentafluorophenyl)borane, NH insertion reaction occurs to synthesize α-amino acid ester compounds, and CH insertion reaction occurs to synthesize diarylacetate compounds. The chemical reaction formula is: ， in: R1 is hydrogen, methyl, halogen; R2 is hydrogen, C1~C5 alkyl, methoxy, halogen, trifluoromethyl; R3 is hydrogen, C1~C3 alkyl, methoxy, halogen, or hydroxyl; n=0、1。 2. The method for synthesizing α-amino acid ester compounds and diarylacetate compounds from oxysulfur ylides and aromatic amines according to claim 1, characterized in that The following preparation steps are adopted: Add oxysulfur ylide, aromatic amine, non-metallic catalyst and solvent into a clean and dry pressure-resistant bottle, seal it, and heat and stir to react; after the reaction is completed, remove the solvent under reduced pressure, and separate and purify by silica gel thin layer chromatography to obtain the product.

3. The method according to claim 2, characterized in that The reaction concentration of oxysulfur ylide was 0.2 mmol / L, and the molar ratio of oxysulfur ylide: aromatic amine: catalyst was 1:1.5:0.

1.

4. The method according to claim 2, characterized in that The reaction temperature of reaction (a) is 50°C, the reaction solvent is chloroform, and the reaction time is 24 hours.

5. The method according to claim 2, characterized in that The reaction temperature of reaction (b) is 80° C., the reaction solvent is 1,2-dichloroethane, and the reaction time is 24 hours.

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