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Synthesis method of (E)-beta-aryl-beta,gamma-unsaturated ester compound

A technology for ester compounds and synthesis methods, which is applied in the preparation of organic compounds, organic chemistry methods, chemical instruments and methods, etc., can solve the problems of difficult and easy control of stereoselectivity, difficult operation of gas raw materials, and the need for metal catalysts. Wide range of compounds, cheap reagents, and high yields

Active Publication Date: 2019-11-22
ANYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although there are many ways to synthesize such compounds, there are also some disadvantages, for example, the use of gas raw materials is not easy to operate, expensive metal catalysts are required, the utilization rate of atoms is low, and stereoselectivity is difficult to control.
More importantly, for compositing ( E )- β -Aryl- beta, gamma - Unsaturated ester compounds still lack effective methods

Method used

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  • Synthesis method of (E)-beta-aryl-beta,gamma-unsaturated ester compound
  • Synthesis method of (E)-beta-aryl-beta,gamma-unsaturated ester compound
  • Synthesis method of (E)-beta-aryl-beta,gamma-unsaturated ester compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] First, put a stir bar in a 35 mL sealed tube, and add 33 μL ethyl diazoacetate (0.3 mmol), 1,4-dioxane (1 mL), 41 μL phenylacetylene (0.36 mmol ), 124.9 mg p-tolueneboronic acid (0.9 mmol), mix well. Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI (0.03 mmol) and 130.0 mg K 3 PO 4 (0.6 mmol). After adding all the medicines, feed nitrogen into the sealed tube for about 3 minutes, remove the air in the sealed tube, seal the tube mouth with a cock, and stir and react at 100° C. for 1.5 hours. After the reaction was finished, the system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extracted with ethyl acetate, the organic phases were combined, the organic phase solvent was removed by distillation under reduced pressure, and the reaction system was subjected to silica gel column chromatography (V 石油醚 :V 乙酸乙酯 =50:1) to obtain 71.0 mg of colorless liquid product 4a, yield 85%. The reaction is shown in the following formula:

[0030...

Embodiment 2

[0037] First, put a stirring bar in a 35 mL sealed tube, and add 33 μL of ethyl diazoacetate (0.3 mmol), 1,4-dioxane (1 mL), 47 μL of p-methylphenylacetylene (0.36 mmol), 124.9 mg p-tolueneboronic acid (0.9 mmol), mix well. Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI (0.03 mmol) and 130.0 mg K 3 PO 4 (0.6 mmol). After adding all the medicines, pass nitrogen into the sealed tube for about 3 minutes, remove the air in the sealed tube, seal the mouth of the tube with a cock, and stir at 100°C for 1.5 hours. After the reaction was finished, the system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extracted with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and the reaction system was subjected to silica gel column chromatography (V 石油醚 :V 乙酸乙酯 =50:1) to obtain 72.0 mg of colorless liquid product 4b (its CAS number is 130240-35-6), with a yield of 8...

Embodiment 3

[0042] First, put a stirring bar in a 35 mL sealed tube, and add 33 μL ethyl diazoacetate (0.3 mmol), 1,4-dioxane (1 mL), 42 μL p-fluorophenylacetylene ( 0.36 mmol), 124.9 mg p-tolueneboronic acid (0.9 mmol), mix well. Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI (0.03 mmol) and 130.0 mg K 3 PO 4 (0.6 mmol). After adding all the medicines, pass nitrogen into the sealed tube for about 3 minutes, remove the air in the sealed tube, seal the mouth of the tube with a cock, and stir at 100°C for 1.5 hours. After the reaction was finished, the system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extracted with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and the reaction system was subjected to silica gel column chromatography (V 石油醚 :V 乙酸乙酯 =50:1) to obtain 63.0 mg of colorless liquid product 4c, yield 70%. The reaction is shown in the following for...

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PUM

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Abstract

The invention belongs to the technical field of organic synthetic chemistry. According to the method, ethyl diazoacetate and arylboronic acid are used as coupling reagents and a 1,1-arylation alkylation reaction is carried out with catalysis of copper, thereby synthesizing the important (E)-beta-aryl-beta,gamma-unsaturated ester in one step. The method specifically comprises the following steps:mixing an alkyne compound, a solvent, ethyl diazoacetate, an arylboronic acid compound, phenanthroline, CuI and K3PO4, then carrying out closed reaction for 1.2-3 hours at 90-110 DEG C in an inert gasatmosphere; and after the reaction is finished, carrying out post-treatment to obtain the product. The method has the characteristics of simple catalytic system, cheap and easily available raw materials, excellent functional group compatibility, high region and chemical selectivity, wide substrate application range and the like, and is suitable for synthesizing various (E)-beta-aryl-beta,gamma-unsaturated ester compounds.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, in particular to a reaction of copper catalyzed alkyne with ethyl diazoacetate and aromatic boronic acid, one-step synthesis ( E )- β -Aryl- beta, gamma - The method of unsaturated ester compounds. Background technique [0002] beta, gamma - Unsaturated ester compounds widely exist in natural products with important biological activities, and at the same time, they are also important organic synthesis intermediates in organic synthesis ((a) Millar, J. G.; Oehlschlager, A. C.; Wong, J.W. J. Org. Chem. 1983, 48 , 4404. (b) Oehlschlager, A. C.; Wong, J. W.; Verigin, V. G.; Pierced, H. D. J. Org. Chem. 1983, 48 , 5009. (c) Liang, J. L.; Javed, U.; Lee, S. H.; Park, J. G.; Jahng, Y. Arch. Pharm. Res. 2014, 37 ,862. (d) Eissler, S.; Nahrwold, M.; Neumann, B.; Stammler, H. G.; Sewald, N. Org. Lett. 2007, 9 , 817.), therefore, the synthetic methods for preparing such com...

Claims

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Application Information

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IPC IPC(8): C07C67/343C07C69/618C07C69/65C07C69/734C07C37/06C07C39/14
CPCC07B2200/09C07C37/06C07C67/343C07C2601/02C07C69/618C07C69/65C07C69/734C07C39/14
Inventor 吕允贺蒲卫亚王薪崔梦行孙金叶刘雪茹
Owner ANYANG NORMAL UNIV
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