A method for synthesizing an allyl sulfonyl compound

Abstract

The application discloses a synthesis method of allyl sulfonyl compounds, and belongs to the technical field of organic synthesis. The method is to use a, beta-unsaturated aldehyde derived sulfonyl hydrazone as raw material, add a base and an organic solvent under the action of a metal catalyst and a ligand, and perform one-pot reaction at a temperature of 70-100 DEG C to obtain the allyl sulfonyl compounds. The method has the advantages of high atom utilization rate, easily obtained raw material, simple operation and short reaction time. The prepared allyl sulfonyl compounds have potential drug activity and biological activity, are important skeletons existing in biological and drug active molecules, and can be used for preparing biological and drug active molecules.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for synthesizing allyl sulfonyl compounds. Background Technology

[0002] The sulfonyl group is an important structural unit in organic chemistry and life science processes, widely found in numerous biologically active natural products and some drug molecules (e.g., eritriptan ([2H]-SB-3CT) for treating migraines and MMP-9 inhibitors for treating prostate cancer). Furthermore, allyl sulfonyl compounds also have wide applications in bioactive molecules (e.g., anticancer agents, cysteine ​​protease inhibitors, antibacterial agents, and herbicides). Therefore, the synthesis of allyl-functionalized sulfonyl compounds has always been a hot topic and a challenging area of ​​research in organic chemistry synthesis. Among the developed strategies for synthesizing allyl-functionalized sulfonyl compounds, two widely used synthetic routes are: (1) direct coupling reaction of alkenyl iodides and hydrazones (J. Org. Chem. 2018, 83, 4762-4768); and (2) coupling reaction of aryl iodides and cinnamaldehyde-derived hydrazones (Chem. Eur. J. 2014, 20, 16093-16096). The limitations of these two methods are that they require additional alkenyl iodides or aryl iodides as reactants to construct the allyl bond. They also suffer from resource waste and low atom utilization, and the reaction operations are complex and time-consuming. Summary of the Invention

[0003] In view of the shortcomings of existing technologies, the purpose of this invention is to provide a method for synthesizing allyl sulfonyl compounds, which requires safe and readily available raw materials, has low cost, is easy to operate, and has high atom utilization.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: a method for synthesizing allyl sulfonyl compounds, characterized in that sulfonylhydrazones derived from α,β-unsaturated aldehydes are used as raw materials, and the allyl sulfonyl compounds are obtained by reacting them in an organic solvent under the combined action of a metal catalyst, ligands and base, followed by post-treatment.

[0005] Furthermore, the reaction formula for the synthesis method is as follows:

[0006]

[0007] In the formula, R 1 Selected from one of aryl and heteroaryl groups; R 2 It is one of the aryl and heteroaryl groups.

[0008] Further, the metal catalyst is palladium acetate, palladium dichloride (di(triphenylphosphine) dichloride), palladium chloride, palladium trifluoroacetate, allyl palladium chloride, palladium dichloride (di(acetonitrile) dichloride), cuprous iodide, copper acetate, or copper trifluoroacetate, with palladium acetate being the preferred metal catalyst.

[0009] Furthermore, the ligand is a triarylphosphine ligand, a trialkylphosphine ligand, a bidentate phosphine ligand derivative, or a nitrogen-containing ligand, preferably a bis(2-diphenylphosphine) ether.

[0010] Further, the alkali is potassium acetate, cesium acetate, potassium carbonate, sodium acetate, potassium tert-butoxide, lithium tert-butoxide, or sodium tert-butoxide, preferably potassium carbonate.

[0011] Furthermore, the organic solvent is ethylene glycol dimethyl ether, dioxane, toluene, tetrahydrofuran, or 1,2-dichloroethane, with 1,2-dichloroethane being the preferred solvent.

[0012] Furthermore, the reaction temperature is 70–100°C, preferably 80°C, and the reaction time is 3–8 hours, preferably 3 hours.

[0013] Further, the molar ratio of the α,β-unsaturated aldehyde-derived sulfonylhydrazone, the metal catalyst, the ligand, and the base is 0.1:0.01:0.02:0.3; and the concentration of the α,β-unsaturated aldehyde-derived sulfonylhydrazone in the mixture containing the organic solvent is 0.1 mol / L.

[0014] Further, the post-processing method is as follows: after the reaction is completed, the organic solvent is removed by rotary evaporation, and the allyl sulfonyl compound is obtained by column chromatography; the eluent for the column chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to 1:1.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0016] (1) This invention uses sulfonylhydrazones derived from α,β-unsaturated aldehydes as a single raw material and synthesizes allyl sulfonyl compounds in one step through the combined action of metal catalysts, ligands and basic compounds, and the attack of metal carbene and nucleophiles. This reaction has the advantages of single and readily available raw materials, low cost, high atom utilization and simple operation.

[0017] (2) The only byproduct of this method is nitrogen, which is environmentally friendly and has no effect on the human body, and is conducive to large-scale production.

[0018] (3) The efficient synthesis of allyl sulfonyl compounds in this invention has broad application prospects in the field of biological and pharmaceutical active molecules (e.g., anticancer agents, cysteine ​​protease inhibitors, antibacterial agents, herbicides). Detailed Implementation

[0019] The present invention will be further described below with reference to the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and should not be used to limit the scope of protection of the present invention.

[0020] This invention provides a method for synthesizing an allyl sulfonyl compound, the reaction formula of which is shown below:

[0021]

[0022] In the formula, R 1 Selected from one of aryl and heteroaryl groups; R 2 It is one of the aryl and heteroaryl groups.

[0023] The specific steps are as follows:

[0024] (1) Add α,β-unsaturated aldehyde-derived sulfonylhydrazone to the reaction tube, and add metal catalyst, ligand, base and solvent in sequence; remove air from the reaction tube, fill with N2, and under stirring, heat to 70-100℃ for reaction, and the reaction time is 3-8 hours.

[0025] (2) The reaction progress was monitored by thin-layer chromatography. The reaction was stopped when there was no raw material in the reaction system. The reaction system was cooled, evaporated under reduced pressure, concentrated, and the residue was mixed with silica gel and separated by column chromatography to obtain allyl sulfonyl compounds. The eluent for column chromatography was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to 1:1.

[0026] Example 1

[0027] Synthesis of (E)-1-methyl-4-((3-(p-tolyl)allyl)sulfonyl)benzene

[0028]

[0029] To a 25 mL reaction flask, 4-tolyl-derived sulfonylhydrazone (65.8 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (385 mg, yield 66%).

[0030] 1H NMR(400MHz,Chloroform-d)δ7.67(dd,J=8.3,1.7Hz,2H),7.23(d,J=8.0Hz,2H),7.13–7.08(m,2H),7.03(d,J=7.8H z,2H),6.26(d,J=15.8Hz,1H),5.96(dtd,J=15.6,7.7,1.6Hz,1H),3.84(d,J=7.6Hz,2H),2.35(s,3H),2.25(s,3H). 13 C NMR(101MHz,Chloroform-d)δ144.80,139.00,138.58,135.55,133.15,129.7 9,129.44,128.61,126.63,114.26,60.70,21.74,21.35.HRMS(ESI)m / z:[M+H] + calcd for C 17 H 19 O2S 287.1100; found:287.1102.

[0031] Example 2

[0032] Synthesis of (E)-1-chloro-4-(3-toluenesulfonylprop-1-en-1-yl)benzene

[0033]

[0034] To a 25 mL reaction flask, 4-chlorophenyl-derived sulfonylhydrazone (69.8 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 3:1) to obtain a colorless liquid (35 mg, yield 57%).

[0035] 1 H NMR(400MHz,Chloroform-d)δ7.73–7.61(m,2H),7.28–7.11(m,6H),6.27(d,J=15 .8Hz, 1H), 5.99 (dt, J=15.8, 7.6Hz, 1H), 3.84 (dd, J=7.6, 1.3Hz, 2H), 2.34 (s, 3H). 13CNMR(101MHz,Chloroform-d)δ144.94,137.79,135.49,134.32,134.22,129.82,128.89,128.49,127.87,116.02,60.45,21.71.HRMS(ESI)m / z:[M+H] + calcd for C 16 H 16 ClO2S307.0554; found:307.0562.

[0036] Example 3

[0037] Synthesis of (E)-1-methoxy-4-(3-toluenesulfonylprop-1-en-1-yl)benzene

[0038]

[0039] To a 25 mL reaction flask, 4-methoxyphenyl-derived sulfonylhydrazone (69.1 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially. The flask was then evacuated and purged with nitrogen. Next, 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (37 mg, yield 62%).

[0040] 1 H NMR(400MHz,Chloroform-d)δ7.67(d,J=7.9Hz,2H),7.23(d,J=8.0Hz,2H),7.18–7.08(m,2H),6.80–6.70(m,2 H),6.25(d,J=15.8Hz,1H),5.93–5.81(m,1H),3.83(dd,J=7.6,1.2Hz,2H),3.72(d,J=0.9Hz,3H),2.35(s,3H). 13 C NMR(101MHz,Chloroform-d)δ159.91,144.77,138.57,135.60,129.77,128.6 8,128.59,127.99,114.10,112.84,60.72,55.38,21.73.HRMS(ESI)m / z:[M+H] + calcd for C 17 H 19O3S 303.1049; found:303.1049.

[0041] Example 4

[0042] Synthesis of (E)-1-methoxy-3-(3-toluenesulfonylprop-1-en-1-yl)benzene

[0043]

[0044] To a 25 mL reaction flask, 3-methoxyphenyl-derived sulfonylhydrazone (69.1 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially. The flask was then evacuated and purged with nitrogen. Next, 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 3:1) to obtain a pale yellow liquid (32 mg, yield 53%).

[0045] 1 H NMR(400MHz,Chloroform-d)δ7.66(d,J=8.0Hz,2H),7.23(d,J=8.0Hz,2H),7.13(dd,J=10.2,6.3Hz,1H),6.79(d,J=7.7Hz,1 H),6.78–6.70(m,2H),6.27(d,J=15.8Hz,1H),6.01(dt,J=15.5,7.5Hz,1H),3.84(d,J=7.6Hz,2H),3.71(s,3H),2.34(s,3H). 13 C NMR(101MHz,Chloroform-d)δ159.80,144.85,138.95,137.25,135.48,129.80,129.7 0,128.54,119.32,115.68,114.09,111.96,60.53,55.29,21.71.HRMS(ESI)m / z:[M+H] + calcd for C 17 H 19 O3S303.1049; found: 303.1049.

[0046] Example 5

[0047] Synthesis of (E)-2-(3-Toluenesulfonylprop-1-en-1-yl)furan

[0048]

[0049] A furanyl-derived sulfonylhydrazone (61.0 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 5 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 3:1) to obtain a colorless liquid (29 mg, yield 55%).

[0050] 1 H NMR(400MHz,Chloroform-d)δ7.68(d,J=7.9Hz,2H),7.33–7.23(m,3H),6.29(dd,J=3.3,1.7Hz,1 H), 6.17 (dd, J=9.6, 6.2Hz, 2H), 5.92 (dt, J=15.6, 7.7Hz, 1H), 3.82 (d, J=7.7Hz, 2H), 2.36 (s, 3H). 13 C NMR(101MHz,Chloroform-d)δ151.51,144.88,142.90,135.63,129.85,128.58,126.79,113.50,111.53,109.78,60.47,21.76.HRMS(ESI)m / z:[M+H] + calcd for C 14 H 15 O3S 263.0736; found:263.0742.

[0051] Example 6

[0052] Synthesis of 2-(cinnamonsulfonyl)-1,3,5-trimethylbenzene

[0053]

[0054] 2,4,6-Trimethyl-N'-((1E,2E)-3-phenylallyl)benzenesulfonylhydrazine (65.7 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (47 mg, yield 79%).

[0055] 1 H NMR(400MHz,Chloroform-d)δ7.16(tq,J=4.3,2.4Hz,5H),6.82(s,2H),6.29(d,J=15.8 Hz,1H),6.00(dt,J=15.6,7.6Hz,1H),3.84(d,J=7.6Hz,2H),2.53(s,6H),2.17(s,3H). 13 C NMR(101MHz,Chloroform-d)δ163.84,139.03,135.90,130.77,130.00,128.75,128.56,126.70,115.58,114.35,60.81,55.77.HRMS(ESI)m / z:[M+H] + calcd forC 18 H 21 O2S 301.1257; found:301.1257.

[0056] Example 7

[0057] Synthesis of 1-(cinnamonsulfonyl)-4-methoxybenzene

[0058]

[0059] 4-Methoxy-N'-((1E,2E)-3-phenylallyl)benzenesulfonylhydrazine (63.2 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 1:1) to obtain a pale yellow liquid (36 mg, yield 63%).

[0060] 1 H NMR(400MHz,Chloroform-d)δ7.72(d,J=8.5Hz,2H),7.23(d,J=5.6Hz,5H),6.90(d,J=8.5Hz, 2H), 6.30 (d, J=15.9Hz, 1H), 6.03 (dt, J=15.6, 7.6Hz, 1H), 3.85 (d, J=7.6Hz, 2H), 3.78 (s, 3H). 13 C NMR(101MHz,Chloroform-d)δ143.36,140.24,138.93,135.84,132.33,132.18,128.63,128.39,126.52,115.10,60.17,23.06.HRMS(ESI)m / z:[M+H] + calcd for C 16 H 17 O3S 289.0893; found:289.0896.

[0061] Example 8

[0062] Synthesis of 2-(cinnamon sulfonyl)naphthalene

[0063]

[0064] N'-((1E,2E)-3-phenylallyl)naphthalene-2-sulfonylhydrazine (67.2 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 4 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (43 mg, 70% yield).

[0065] 1 H NMR(400MHz,Chloroform-d)δ8.38(d,J=1.8Hz,1H),7.91–7.81(m,3H),7.76(dd,J=8.6,1.9Hz,1H),7.59–7 .49(m,2H),7.22–7.13(m,5H),6.31(d,J=15.9Hz,1H),6.04(dt,J=15.5,7.6Hz,1H),3.94(d,J=7.6Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ139.32,135.76,135.42,135.36,132.12,130.40,129.48,129 .36,128.68,128.55,128.02,127.73,126.66,123.19,115.13,60.60.HRMS(ESI)m / z:[M+H] + calcd for C 19 H 17 O2S309.0944; found: 309.0951.

[0066] Example 9

[0067] Synthesis of 5-(cinnamylsulfonyl)-N,N-dimethylnaphthalene-1-amine

[0068]

[0069] 5-(dimethylamino)-N'-((1E,2E)-3-phenylallyl)naphthalene-1-sulfonylhydrazine (75.8 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (48 mg, yield 69%).

[0070] 1 H NMR(400MHz,Chloroform-d)δ8.54–8.48(m,1H),8.39(d,J=8.6Hz,1H),8.16(dd,J=7.3,1.3Hz,1H),7.54(dd,J=8.7,7.6Hz,1H),7.46(d d,J=8.5,7.3Hz,1H),7.19–7.10(m,6H),6.22(d,J=15.8Hz,1H),5.98(dt,J=15.5,7.5Hz,1H),4.09(dd,J=7.5,1.2Hz,2H),2.82(s,6H). 13 C NMR(101MHz,Chloroform-d)δ152.23,139.07,135.86,133.82,131.56,131.29,130.57,129.82,128.86 ,128.67,128.63,128.47,126.67,123.46,118.60,115.35,115.22,59.95,45.49.HRMS(ESI)m / z:[M+H] + calcd for C 21 H 22 NO2S 352.1366; found:352.1368.

[0071] Example 10

[0072] Synthesis of (cinnamon sulfonyl)benzene

[0073]

[0074] N'-((1E,2E)-3-phenylallyl)benzenesulfonylhydrazine (57.2 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (37 mg, yield 72%).

[0075] 1 H NMR(400MHz,Chloroform-d)δ7.81(dd,J=8.1,1.6Hz,2H),7.60–7.54(m,1H),7.49–7.43(m,2H),7. 26–7.18(m,5H),6.29(d,J=15.8Hz,1H),6.03(dt,J=15.6,7.6Hz,1H),3.88(dd,J=7.6,1.3Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ139.34,138.43,135.83,133.92,129.22,128.79,128.66,128.64,126.73,115.19,60.60.HRMS(ESI)m / z:[M+H] + calcd for C 15 H 15 O2S 259.0787; found:259.0789.

[0076] Example 11

[0077] Synthesis of 1-chloro-3-(cinnamon sulfonyl)benzene

[0078]

[0079] 3-Chloro-N'-((1E,2E)-3-phenylallyl)benzenesulfonylhydrazine (64.0 mg, 0.2 mmol), palladium acetate (4.48 mg, 0.02 mmol), bis(2-diphenylphosphine) ether (21.6 mg, 0.04 mmol), and potassium carbonate (41.4 mg, 0.3 mmol) were added sequentially to a 25 mL reaction flask. The flask was then evacuated and purged with nitrogen. 2.0 mL of 1,2-dichloroethane was added, the flask was sealed, and the mixture was stirred in an oil bath at 80 °C for 3 hours. After the reaction was complete, the solvent was removed by rotary evaporation, followed by column chromatography (petroleum ether / ethyl acetate = 2:1) to obtain a pale yellow liquid (30 mg, yield 51%).

[0080] 1 H NMR(400MHz,Chloroform-d)δ7.81(d,J=2.0Hz,1H),7.68(dd,J=7.8,1.6Hz,1H),7.53(dd,J=8.0,2.1Hz,1H),7.3 9(t,J=7.9Hz,1H),7.27–7.18(m,5H),6.34(d,J=15.8Hz,1H),6.01(dt,J=15.6,7.6Hz,1H),3.89(d,J=7.6Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ140.05,139.75,135.56,135.48,134.02,130.43 ,128.75,128.73,128.59,126.79,126.69,114.57,60.49.HRMS(ESI)m / z:[M+H] + calcd for C 15 H 14 ClO2S 293.0398; found:293.0401.

[0081] The allyl sulfonyl compounds obtained in this invention are important backbones widely found in biological and pharmaceutical active molecules, such as cysteine ​​protease inhibitors, with the following structural formula:

[0082]

[0083] Example 10 (cinnamylsulfonyl)benzene (CAS: 16212-06-9) has potential biological and pharmaceutical activities, and this compound is an important molecular intermediate in the fields of biological and chemical research.

[0084] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent substitutions, and improvements made by those skilled in the art to the above embodiments without departing from the scope of the technical solution of the present invention, based on the technical essence of the present invention, shall still fall within the protection scope of the technical solution of the present invention.

Claims

1. A method for synthesizing an allyl sulfonyl compound, characterized in that, Using sulfonylhydrazones derived from α,β-unsaturated aldehydes as raw materials, allyl sulfonyl compounds can be obtained by reacting them in an organic solvent under the combined action of a metal catalyst, ligands, and a base, followed by post-treatment. The reaction formula of the synthetic method is as follows: ， In the formula, R 1 Selected from one of aryl and heteroaryl groups; R 2 The metal catalyst is palladium acetate, and the ligand is bis(2-diphenylphosphine) ether. The base is potassium acetate, cesium acetate, potassium carbonate, sodium acetate, potassium tert-butoxide, lithium tert-butoxide, or sodium tert-butoxide. The reaction temperature is 70-100℃.

2. The method for synthesizing allyl sulfonyl compounds according to claim 1, characterized in that, The organic solvent is ethylene glycol dimethyl ether, dioxane, toluene, tetrahydrofuran, or 1,2-dichloroethane.

3. The method for synthesizing allyl sulfonyl compounds according to claim 1, characterized in that, The reaction time is 3 to 8 hours.

4. The method for synthesizing allyl sulfonyl compounds according to claim 1, characterized in that, The molar ratio of the α,β-unsaturated aldehyde-derived sulfonylhydrazone, the metal catalyst, the ligand, and the base is 0.1:0.01:0.02:0.3; the concentration of the α,β-unsaturated aldehyde-derived sulfonylhydrazone in the mixture containing the organic solvent is 0.1 mol / L.

5. The method for synthesizing allyl sulfonyl compounds according to claim 1, characterized in that, The post-processing method is as follows: after the reaction is completed, the organic solvent is removed by rotary evaporation, and the allyl sulfonyl compounds are obtained by column chromatography; the eluent for the column chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to 1:1.

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