Preparation method of diaryl dicarbonyl substituted olefin

Abstract

The invention discloses a preparation method of diaryl dicarbonyl substituted olefin, which comprises the following steps: (1) in a nitrogen atmosphere, mixing tri-substituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphine-2-(N, N-dimethylamine)-biphenyl, alkali, norbornene and an organic solvent, reacting at 100-120 DEG C for 20-24 hours, and then cooling to room temperature; (2) diluting the material obtained in the step (1) with ethyl acetate, washing with water, and separating to obtain an organic phase; and (3) sequentially carrying out drying, filtering, concentration and column chromatography purification on the organic phase obtained in the step (2) to obtain the diaryl dicarbonyl substituted olefin. According to the invention, ortho-position alkenylation of iodobenzene is realized through Catellai reaction, a simple and efficient strategy is provided for synthesis of diaryl dicarbonyl substituted olefin, and the method has a wide application prospect in the fields of synthetic chemistry and medicinal chemistry.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a method for preparing diaryldicarbonyl substituted olefins. Background Art

[0002] Tetrasubstituted olefins are very important organic building blocks and are widely used in the fields of medicine, natural products and materials. Conventional synthetic methods can usually only synthesize mono-, di- or tri-substituted olefins, such as Heck reaction, free radical addition / elimination reaction and transition metal palladium-catalyzed coupling reaction of aryl halides with alkenyl metal reagents. These methods are not suitable for the synthesis of tetrasubstituted complex olefins. Therefore, it is of great significance to develop new synthetic routes to prepare tetrasubstituted olefins, such as diaryldicarbonyl substituted olefins. Summary of the invention

[0003] The present invention aims to overcome the defects of the prior art and provide a method for preparing diaryldicarbonyl substituted olefins.

[0004] The technical solution of the present invention is as follows:

[0005] A method for preparing a diaryldicarbonyl substituted olefin comprises the following steps:

[0006] (1) under a nitrogen atmosphere, trisubstituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl, base, norbornene and an organic solvent are mixed, reacted at 100-120° C. for 20-24 hours, and then cooled to room temperature;

[0007] The structural formula of the above aryl iodide is wherein R is methyl, methoxy, phenyl or trifluoromethyl;

[0008] The structural formula of the above monosubstituted olefin is wherein R1 is an ester group, an aryl group or a sulfonyl group;

[0009] The structural formula of the above trisubstituted vinyl bromide is Wherein R2 is an alkyl group or an aryl group;

[0010] The structural formula of the above-mentioned norbornene is

[0011] (2) diluting the material obtained in step (1) with ethyl acetate, washing with water, and separating the organic phase;

[0012] (3) The organic phase obtained in step (2) is dried, filtered, concentrated and purified by column chromatography to obtain the diaryldicarbonyl substituted olefin.

[0013] In a preferred embodiment of the present invention, the molar ratio of the trisubstituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphino-2`-(N,N-dimethylamino)-biphenyl, base and norbornene is 0.08-0.12: 0.1-0.13: 0-0.15: 0.005-0.014: 0.015-0.024: 0.35-0.44: 0.25-0.34.

[0014] Further preferably, when the monosubstituted olefin is 0, the diaryldicarbonyl substituted olefin is cyclic and has the structural formula The reaction formula is

[0015]

[0016] Further preferably, when the monosubstituted olefin is not 0, the diaryldicarbonyl substituted olefin is chain-shaped, and its structural formula is The reaction formula is

[0017]

[0018] In a preferred embodiment of the present invention, the base is selected from potassium bicarbonate, potassium tert-butoxide, sodium carbonate, potassium carbonate, potassium phosphonate and cesium carbonate.

[0019] More preferably, the base is potassium carbonate.

[0020] In a preferred embodiment of the present invention, the organic solvent is selected from toluene, 1,2-dichloroethane, acetonitrile, 1,4-dioxane, tetrahydrofuran and N,N-dimethylformamide.

[0021] More preferably, the organic solvent is potassium carbonate.

[0022] In a preferred embodiment of the present invention, the molar ratio of the trisubstituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphino-2`-(N,N-dimethylamino)-biphenyl, base and norbornene is 0.1:0.12:0-0.15:0.01:0.02:0.4:0.3.

[0023] More preferably, the organic solvent corresponding to every 0.1 mmol of the tri-substituted vinyl bromide compound is 1 mL.

[0024] The beneficial effects of the present invention are:

[0025] 1. The present invention realizes the ortho-olefination of iodobenzene through the Catellani reaction, providing a simple and efficient strategy for the synthesis of diaryldicarbonyl substituted olefins, which has broad application prospects in the fields of synthetic chemistry and medicinal chemistry.

[0026] 2. During the synthesis process, the present invention can synthesize chain diaryl dicarbonyl substituted olefin compounds in the presence of a terminating agent, and can synthesize cyclic diaryl dicarbonyl substituted olefin compounds in the absence of a terminating agent.

[0027] 3. The product yield of the present invention is high, the substrate has a wide range of application, the reaction has strong specificity, the post-treatment process is simple and meets the requirements of green environmental protection. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0029] Example 1

[0030] This embodiment relates to the preparation of diethyl (E)-2-{[2-(3-methoxy-3-oxoprop-1-en-1-yl)-3-methylphenyl](o-tolyl)methylene}malonate compound, the structural formula of which is:

[0031]

[0032] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), o-methyliodobenzene (0.1mmol, 1.0equiv), methyl acrylate (0.15mmol, 1.5equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 37.7 mg of the target product with a yield of 82%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.44(d,J=16.2Hz,1H),7.17(d,J=17.0Hz,4H),6.90-7.10(m,2H),6.95(s,1H ),6.12(d,J=16.2Hz,1H),4.08–3.97(m,4H),3.77(s,3H),2.25(s,3H),2.08(s,3H),0.97(q,J=7.5Hz,6H). 13C NMR(126MHz,Chloroform-d)δ166.56,165.69,165.22,143.25,138.09,136.88,136.21,133.96,131.06,131.03,130.50,129 .71,128.71,128.07(d,J=4.4Hz),127.78,125.05,125.03,125.01,124.82,61.24,61.19,51.61,20.68,20.20,13.59,13.57.

[0033] Example 2

[0034] This embodiment relates to the preparation of diethyl (E)-2-{[3-methoxy-2-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl](o-tolyl)methylene}malonate compound, the structural formula of which is:

[0035]

[0036] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), o-iodoanisole (0.1mmol, 1.0equiv), methyl acrylate (0.15mmol, 1.5equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 33.9 mg of the target product with a yield of 75%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.73(d,J=16.1Hz,1H),7.26(d,J=16.1Hz,1H),7.17(t,J=8.0Hz,1H),7.09(q,J=8.0,7.3Hz,3 H),6.80-6.70(m,2H),6.69(d,J=16.1Hz,1H),4.06-3.97(m,4H),3.85(s,3H),3.76(s,3H),2.21(s,3H),1.21-0.92(m,6H).13 C NMR(126MHz,Chloroform-d)δ167.78,165.16,165.02,158.98,154.35,139.00,138.67,135.98,130.61,130.47,129.75,129.72, 128.72,125.35,123.07,122.38–122.19(m),121.95,111.32,111.25,61.27,61.24,55.56,51.50,20.59–19.91(m),13.65,13.55.

[0037] Example 3

[0038] This embodiment relates to the preparation of diethyl (E)-2-{[4-chloro-2-(3-methoxy-3-oxoprop-1-en-1-yl)-3-methylphenyl](o-tolyl)methylene}malonate compound, the structural formula of which is:

[0039]

[0040] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), 1-chloro-3-iodo-2-methylbenzene (0.1mmol, 1.0equiv), methyl acrylate (0.15mmol, 1.5equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 40.5 mg of the target product with a yield of 86%. The target product was characterized by NMR: 1H NMR(500MHz,Chloroform-d)δ7.38(d,J=16.2Hz,1H),7.22–7.15(m,3H),7.12–7.02(m,2H),6.94(s,1H),6.11(d,J=16.2Hz,1H), 4.10(q,J=7.1Hz,2H),4.01(q,J=7.1Hz,2H),3.76(s,3H),2.24(s,3H),2.11(s,3H),1.06(t,J=7.1Hz,3H),0.95(t,J=7.3Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ166.33,165.18,164.93,141.96,138.81,137.48,136.17,133.50,132.49,130.69,130.65,130.48, 130.44,128.97,127.63,127.70–127.53(m),125.32,125.23,125.21,61.47,61.32,51.70,20.68,20.30–19.99(m),13.69,13.54.

[0041] Example 4

[0042] This embodiment relates to the preparation of diethyl (E)-2-{[1-(3-methoxy-3-oxoprop-1-en-1-yl)naphthalen-2-yl](o-tolyl)methylene}malonate compound, the structural formula of which is:

[0043]

[0044] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010 mmol, 10 mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02 mmol, 20 mol%), potassium carbonate (0.3 mmol, 3.0 equiv), norbornene (0.3 mmol, 3.0 equiv), 1-iodonaphthalene (0.1 mmol, 1.0 equiv), methyl acrylate (0.15 mmol, 1.5 equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12 mmol, 1.2 equiv) and 1,4-dioxane (1.0 mL) are added to a 15 mL Shrek tube. The Shrek tube is sealed and stirred at 100° C. for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography to obtain 24.1 mg of the target product, with a yield of 51%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.98(d,J=8.0Hz,1H),7.87–7.77(m,3H),7.53–7.46(m,2H),7.43(d,J=8.5Hz,1H),7.23-7.16(m,1H), 7.13-7.02(m,3H),6.27(d,J=16.1Hz,1H),4.20-4.02(m,4H),3.82(s,3H),2.10(s,3H),0.97(t,J=7.1Hz,3H),0.90(t,J=7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ166.35,165.35,153.15,142.29,138.52,136.15,135.52,133.27,132.14,132.11,131.18,131.16,13 1.11,130.57,130.55,130.45,128.85,128.32,126.97,126.78,126.50,125.38,125.13,61.35,61.27,51.73,20.36,13.61,13.57.

[0045] Example 5

[0046] This embodiment relates to the preparation of diethyl (E)-2-{[2-methoxy-3-(3-methoxy-3-oxoprop-1-en-1-yl)pyridin-4-yl](o-tolyl)methylene}malonate compound, and its structural formula is:

[0047]

[0048] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), 3-iodo-2-methoxypyridine (0.1mmol, 1.0equiv), methyl acrylate (0.15mmol, 1.5equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 22.6 mg of the target product with a yield of 52%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.98(d,J=8.0Hz,1H),7.87–7.77(m,3H),7.53–7.46(m,2H),7.43(d,J=8.5Hz,1H),7.23-7.16(m,1H), 7.13-7.02(m,3H),6.27(d,J=16.1Hz,1H),4.20-4.02(m,4H),3.82(s,3H),2.10(s,3H),0.97(t,J=7.1Hz,3H),0.90(t,J=7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ166.35,165.35,153.15,142.29,138.52,136.15,135.52,133.27,132.14,132.11,131.18,131.16,13 1.11,130.57,130.55,130.45,128.85,128.32,126.97,126.78,126.50,125.38,125.13,61.35,61.27,51.73,20.36,13.61,13.57.

[0049] Example 6

[0050] This embodiment relates to the preparation of diethyl (E)-2-{[4-(3-methoxy-3-oxoprop-1-en-1-yl)dibenzo[b,d]furan-3-yl](o-tolyl)methylene}malonate compound, and its structural formula is:

[0051]

[0052] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010 mmol, 10 mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02 mmol, 20 mol%), potassium carbonate (0.3 mmol, 3.0 equiv), norbornene (0.3 mmol, 3.0 equiv), 4-iododibenzo[b,d]furan (0.1 mmol, 1.0 equiv), methyl acrylate (0.15 mmol, 1.5 equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12 mmol, 1.2 equiv) and 1,4-dioxane (1.0 mL) are added to a 15 mL Shrek tube. The Shrek tube is sealed and stirred at 100° C. for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography to obtain 28.2 mg of the target product with a yield of 52%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ8.04(d,J=16.0Hz,1H),7.94(d,J=6.3Hz,1H),7.88(d,J=8.1Hz,1H),7.64(d,J=8.3Hz,1H),7.52–7.49(m,1H),7.42–7.34(m ,1H),7.28(s,1H),7.25–7.11(m,5H),4.06(q,J=7.2Hz,2H),3.98(q,J=7.1Hz ,2H),3.85(s,3H),2.26(s,3H),0.98(t,J=7.1Hz,3H),0.94(t,J=7.1Hz,3H). 13C NMR(126MHz,Chloroform-d)δ167.52,165.14,164.76,156.58,154.56,153.44,139.37,139.34,137.26,131.35,130.78,129.22,128.96,12 7.99,125.65,125.28,124.65,123.81,123.40,123.16,121.27,120.8 2,118.31,118.30,111.99,61.42,61.34,51.78,20.17,13.59,13.56.

[0053] Example 7

[0054] This embodiment relates to the preparation of diethyl (E)-2-{[3-methyl-2-(3-oxo-3-phenoxyprop-1-en-1-yl)phenyl](o-tolyl)methylene}malonate compound, the structural formula of which is:

[0055]

[0056] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), o-methyliodobenzene (0.1mmol, 1.0equiv), phenyl acrylate (0.15mmol, 1.5equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 32.5 mg of the target product with a yield of 65%. The target product was characterized by NMR: 1H NMR(500MHz,Chloroform-d)δ7.66(d,J=16.2Hz,1H),7.45–7.38(m,1H),7.28–7.24(m,2H),7.21–7.07(m,6H),6.31(d,J=16 .2Hz,1H),4.07(q,J=7.1Hz,2H),4.05–3.99(m,5H),2.33(s,3H),2.13(s,5H),1.01(t,J=7.1Hz,3H),0.97(t,J=7.4Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ165.68,165.25,164.46,150.73,144.95,138.16,137.01,136.30,133.68,131.22,130.62,130.57,129.98,12 9.96,129.94,129.44,128.84,128.28,128.11,125.80,125.18,125.1 7,124.27,121.56,121.49,61.32,61.25,20.82,20.25,13.64,13.58.

[0057] Example 8

[0058] This embodiment relates to the preparation of diethyl (E)-2-{[3-methyl-2-(3-oxo-3-phenoxyprop-1-en-1-yl)phenyl](o-tolyl)methylene}malonate compound, the structural formula of which is:

[0059]

[0060] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), o-methyliodobenzene (0.1mmol, 1.0equiv), 1-penten-3-one (0.15mmol, 1.5equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 33.5 mg of the target product with a yield of 77%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.35(d,J=16.4Hz,1H),7.20–7.14(m,3H),7.09–7.02(m,2H),6.97–6.91(m,1H),6.38(d,J= 16.5Hz,1H),4.08–3.97(m,3H),2.55(q,J=7.4Hz,2H),2.26(s,3H),2.06(s,3H),1.11(t,J=7.3Hz,3H),1.02-0.92(m,6H). 13 C NMR(126MHz,Chloroform-d)δ200.49,165.52,165.30,140.56,138.43,136.83,136.20,134.15,134.14,133.09,131.12,130.6 2,130.61,129.91,128.79,128.07,127.82,125.17,125.15,61.30,61.22,33.45,20.81,20.46–19.56(m),13.62,13.58,8.07.

[0061] Example 9

[0062] This embodiment relates to the preparation of diethyl (E)-2-({3-methyl-2-[2-(phenylsulfonyl)vinyl]phenyl}(o-tolyl)methylene)malonate compound, the structural formula of which is:

[0063]

[0064] The preparation specifically includes: in a nitrogen atmosphere, palladium acetate (0.010 mmol, 10 mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02 mmol, 20 mol%), potassium carbonate (0.3 mmol, 3.0 equiv), norbornene (0.3 mmol, 3.0 equiv), o-methyliodobenzene (0.1 mmol, 1.0 equiv), phenyl vinyl sulfone (0.15 mmol, 1.5 equiv), diethyl 2-(bromo(O-tolyl)methylene)malonate (0.12 mmol, 1.2 equiv) and 1,4-dioxane (1.0 mL) are added to a 15 mL Shrek tube. The Shrek tube is sealed and stirred at 100° C. for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 25.9 mg of the target product with a yield of 50%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.89(d,J=7.7Hz,2H),7.61(t,J=7.3Hz,1H),7.57–7.48(m,3H),7.23–7.14(m,4H),7.12–7. 01(m,2H),6.92(d,J=7.8Hz,1H),6.75(d,J=15.6Hz,1H),4.05–3.96(m,4H),2.22(s,3H),2.07(s,3H),1.01–0.91(m,6H). 13 C NMR(126MHz,Chloroform-d)δ165.34,164.88,155.42,140.54,140.36,137.74,137.20,136.20,133.66,133.60,133.38,131.45,131.1 7,131.13,130.74,130.20,129.35,129.28,128.91,128.47,128.34,128.31,127.81,125.46,61.34,61.24,20.74,20.56,13.65,13.57.

[0065] Example 10

[0066] This embodiment relates to the preparation of diethyl (E)-2-{[2-(3-methoxy-3-oxoprop-1-en-1-yl)-3-methylphenyl](2-methoxyphenyl)methylene}malonate compound, and its structural formula is:

[0067]

[0068] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), o-methyliodobenzene (0.1mmol, 1.0equiv), methyl acrylate (0.15mmol, 1.5equiv), diethyl 2-(bromo(2-methoxyphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 18.1 mg of the target product with a yield of 40%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.32(d,J=16.1Hz,1H),7.26–7.18(m,2H),7.21–7.15(m,2H),6.79–6.71(m,2H),6.67–6.61(m,1H),6.37(d,J =16.0Hz,1H),4.08(q,J=7.1Hz,2H),4.04–3.98(m,2H),3.73(s,3H),3.67(s,3H),2.24(s,3H),1.08(t,J=7.1Hz,3H),0.91(t,J=7.2Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ166.87,166.53,165.15,155.87,150.93,141.89,141.17,137.26,133.88,130.68,130.4 4,130.30,129.07,127.88,127.50,124.70,119.96,113.34,109.73,61.01,60.81,54.64,51.35,20.33,13.80,13.51.

[0069] Embodiment 11

[0070] The structural formula of the target product involved in this embodiment is

[0071] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010mmol, 10mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02mmol, 20mol%), potassium carbonate (0.3mmol, 3.0equiv), norbornene (0.3mmol, 3.0equiv), o-methyliodobenzene (0.1mmol, 1.0equiv), diethyl 2-(bromo(O-methylphenyl)methylene)malonate (0.12mmol, 1.2equiv) and 1,4-dioxane (1.0mL) are added to a 15mL Shrek tube. The Shrek tube is sealed and stirred at 100°C for 24h. After cooling to room temperature, the reaction solution is diluted with ethyl acetate, then washed with water three times, and the organic phase is dried with anhydrous Na2SO4, and then filtered, concentrated and purified by column chromatography to obtain 15.6mg of the target product, with a yield of 51%. The NMR characterization of the target product is: 1 H NMR(500MHz,Chloroform-d)δ7.39–7.29(m,3H),7.25(t,J=7.5Hz,1H),7.20–7.18(m,2H),6 .72(d,J=7.2Hz,1H),4.14(q,J=7.1Hz,2H),2.63(s,3H),2.25(s,3H),1.09(t,J=7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ193.35,167.09,162.42,144.00,138.47,135.04,134.57,132 .96,130.15,129.04,126.86,126.59,125.54,124.52,121.41,60.50,19.86,17.27,13.84.

[0072] Example 12

[0073] The structural formula of the target product involved in this embodiment is

[0074] The preparation specifically includes: under nitrogen atmosphere, palladium acetate (0.010 mmol, 10 mol%), 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl (0.02 mmol, 20 mol%), potassium carbonate (0.3 mmol, 3.0 equiv), norbornene (0.3 mmol, 3.0 equiv), o-methyliodobenzene (0.1 mmol, 1.0 equiv), diethyl 2-(bromo(2-methoxynaphthalen-1-yl)methylene)malonate (0.12 mmol, 1.2 equiv) and 1,4-dioxane (1.0 mL) are added to a 15 mL Shrek tube. The Shrek tube is sealed and stirred at 100° C. for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, then washed three times with water, and the organic phase was dried over anhydrous Na2SO4, filtered, concentrated and purified by column chromatography to obtain 17.4 mg of the target product with a yield of 47%. The target product was characterized by NMR: 1 H NMR(500MHz,Chloroform-d)δ7.99(d,J=9.0Hz,1H),7.91–7.83(m,1H),7.62–7.56(m,1H),7.45–7.37(m,3H), 7.21–7.13(m,2H),6.63–6.57(m,1H),3.99(q,J=7.1Hz,2H),3.90(s,3H),2.67(s,3H),0.83(t,J=7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ193.40,163.72,162.37,153.38,144.07,138.17,134.27,132.88,131.47,131.05 ,128.75,128.22,127.01,126.87,126.60,124.52,123.98,121.40,115.60,112.96,60.13,56.54,17.32,13.61.

[0075] The above description is only a preferred embodiment of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A method for preparing a diaryldicarbonyl substituted olefin, characterized in that: The steps include: (1) under a nitrogen atmosphere, trisubstituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl, base, norbornene and an organic solvent are mixed, reacted at 100-120° C. for 20-24 hours, and then cooled to room temperature; The structural formula of the above aryl iodide is wherein R is methyl, methoxy, phenyl or trifluoromethyl; The structural formula of the above monosubstituted olefin is wherein R1 is an ester group, an aryl group or a sulfonyl group; The structural formula of the above trisubstituted vinyl bromide is Wherein R2 is an alkyl group or an aryl group; The structural formula of the above-mentioned norbornene is (2) diluting the material obtained in step (1) with ethyl acetate, washing with water, and separating the organic phase; (3) The organic phase obtained in step (2) is dried, filtered, concentrated and purified by column chromatography to obtain the diaryldicarbonyl substituted olefin.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the trisubstituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl, base and norbornene is 0.08-0.12: 0.1-0.13: 0-0.15: 0.005-0.014: 0.015-0.024: 0.35-0.44: 0.25-0.

34.

3. The preparation method according to claim 2, characterized in that: When the monosubstituted olefin is 0, the diaryldicarbonyl substituted olefin is cyclic, and its structural formula is 4. The preparation method according to claim 2, characterized in that: When the monosubstituted olefin is not 0, the diaryldicarbonyl substituted olefin is chain-like, and its structural formula is 5. The preparation method according to any one of claims 1 to 4, characterized in that: The base is selected from potassium bicarbonate, potassium tert-butoxide, sodium carbonate, potassium carbonate, potassium phosphonate and cesium carbonate.

6. The preparation method according to claim 5, characterized in that: The base is potassium carbonate.

7. The preparation method according to any one of claims 1 to 4, characterized in that: The organic solvent is selected from toluene, 1,2-dichloroethane, acetonitrile, 1,4-dioxane, tetrahydrofuran and N,N-dimethylformamide.

8. The preparation method according to claim 7, characterized in that: The organic solvent is potassium carbonate.

9. The preparation method according to any one of claims 1 to 4, characterized in that: The molar ratio of the trisubstituted vinyl bromide, aryl iodide, monosubstituted olefin, palladium acetate, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl, base and norbornene is 0.1:0.12:0-0.15:0.01:0.02:0.4:0.

3.

10. The preparation method according to claim 9, characterized in that: The organic solvent corresponds to 1 mL per 0.1 mmol of the tri-substituted vinyl bromide compound.

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