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Preparation method of alpha, alpha, alpha-trisubstituted ester derivative

A technology of ester derivatives and three substitutions, which is applied in the field of preparation of α,α,α-trisubstituted ester derivatives, can solve the problems of difficult cutting and sewing, harsh reaction conditions, long reaction time, etc. The effect of simple processing and simple raw materials

Active Publication Date: 2020-05-19
HUAQIAO UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Existing methods usually require cumbersome steps to obtain α,α,α-trisubstituted ester derivatives, it is difficult to effectively realize the "cutting and stitching" of the C(CO)-C bond, and there are usually low yields, reaction A series of problems such as harsh conditions and long response time

Method used

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  • Preparation method of alpha, alpha, alpha-trisubstituted ester derivative
  • Preparation method of alpha, alpha, alpha-trisubstituted ester derivative
  • Preparation method of alpha, alpha, alpha-trisubstituted ester derivative

Examples

Experimental program
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Effect test

Embodiment 1

[0023] Preparation of (E)-1-methoxy-1,5-dioxo-5-phenyl-2-(p-tolyl)pent-3-en-2-ylbenzoate

[0024]

[0025] Add 0.1mmol of 2-diazoaryl acetate compound, 0.2mmol of 1,3-diphenylpropane-1,3-dione, Type molecular sieve 50mg, 0.5mL nitrogen nitrogen dimethyl formamide, finally add 2mol% rhodium acetate. Air atmosphere, at room temperature, after stirring for 12 h, filtered through diatomaceous earth, concentrated, and purified by column chromatography to obtain 27.3 mg of the target product with a yield of 66%. The NMR characterization of this compound is as follows: 1 H NMR (500MHz, Chloroform-d) δ=8.22–8.17(m,2H),7.86–7.80(m,3H),7.68–7.63(m,1H),7.56–7.50(m,5H),7.42(dd ,J=8.3,7.1,2H),7.26(s,2H),6.90(d,J=16.0,1H),3.78(s,3H),2.38(s,3H); 13 C NMR (126MHz, Chloroform-d) δ190.8, 169.4, 164.9, 145.1, 139.0, 137.4, 134.2, 133.8, 132.9, 130.0, 129.6, 129.2, 128.8, 128.7, 128.5, 126.4, 125.8, 82.1, 1.53.

Embodiment 2

[0027] Preparation of (E)-1-ethoxy-1,5-dioxocarbonyl-2,5-diphenylpent-3-en-2-ylbenzoate

[0028]

[0029] Add 0.1mmol of 2-diazoaryl acetate compound, 0.2mmol of 1,3-diphenylpropane-1,3-dione, Type molecular sieve 50mg, 0.5mL nitrogen nitrogen dimethyl formamide, finally add 2mol% rhodium acetate. Air atmosphere, at room temperature, after stirring for 12 h, filtered through diatomaceous earth, concentrated, and purified by column chromatography to obtain 35.9 mg of the target product with a yield of 87%. The NMR characterization of this compound is as follows: 1 H NMR (500MHz, Chloroform-d) δ8.23–8.16(m,2H),7.89–7.83(m,2H),7.82(d,J=1.5,1H),7.70–7.63(m,3H),7.53 (td, J=7.6,1.5,3H),7.48–7.36(m,5H),6.90(d,J=15.9,1H),4.32–4.19(m,2H),1.21(t,J=7.1,3H ); 13 C NMR (126MHz, Chloroform-d) δ190.8, 168.7, 164.8, 145.1, 137.4, 137.3, 133.7, 132.9, 130.0, 129.3, 128.9, 128.8, 128.8, 128.7, 128.5, 126.6, 125.9, 84, 13.6, 629.

Embodiment 3

[0031] Preparation of (E)-1-methoxy-2-(4-methoxyphenyl)-1,5-dioxo-5-phenylpent-3-en-2-ylbenzoate

[0032]

[0033] Add 0.1mmol of 2-diazoaryl acetate compound, 0.2mmol of 1,3-diphenylpropane-1,3-dione, Type molecular sieve 50mg, 0.5mL nitrogen nitrogen dimethyl formamide, finally add 2mol% rhodium acetate. Air atmosphere, at room temperature, after stirring for 12 h, filtered through celite, concentrated, and purified by column chromatography to obtain 32.9 mg of the target product with a yield of 77%. The NMR characterization of this compound is as follows: 1 H NMR (500MHz, Chloroform-d) δ8.19 (dt, J=8.2,1.1,2H),7.89–7.79(m,3H),7.68–7.62(m,1H),7.59–7.55(m,2H) ,7.53(td,J=7.5,4.3,3H),7.42(t,J=7.7,2H),6.99–6.90(m,3H),3.83(s,3H),3.78(s,3H); 13C NMR (126MHz, Chloroform-d) δ190.7,169.4,164.9,160.0,145.1,137.4,133.7,132.9,130.0,129.3,129.1,128.7,128.6,128.5,127.5,126.5,114.2,83.3,53.5

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Abstract

The invention discloses a preparation method of an alpha, alpha, alpha-trisubstituted ester derivative, which comprises the following steps: sequentially mixing 1,3-diketone, 2-diazoacetate, a metal catalyst, a drying agent and an amide organic solvent, and carrying out a reaction at room temperature; filtering the reaction product to separate solid impurities, and washing the reaction product with dichloromethane for multiple times to obtain a filtrate; and concentrating the obtained filtrate, and carrying out column chromatography or thin-layer chromatography to obtain the alpha, alpha, alpha-trisubstituted ester derivative. According to the invention, by means of a relatively simple substrate and a simple and convenient process, the alpha, alpha, alpha-trisubstituted ester derivative which requires complex steps in a conventional method is prepared, wherein the steric hindrance between substrates is overcome, the substrate universality is good, the yield is high, the reaction conditions are mild, the reaction time is short, raw materials are simple and easy to obtain, the atom utilization rate is high, and experimental post-treatment is simple and environmentally friendly.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of α, α, α-trisubstituted ester derivatives. Background technique [0002] Ketones are widely found in natural products and synthetic molecules, and are one of the most basic raw materials in organic synthesis. Although there are many reactions involving the α-functionalization transformation of the carbonyl group of ketones, the selective cleavage of C(CO)-C remains a great challenge. In particular, the direct insertion of functional groups into the C(CO)–C single bond can form novel compounds that are difficult to obtain by other methods. Therefore, the C(CO)–C insertion reaction is of great importance both in practical synthetic applications and in mechanistic studies. Existing methods usually require cumbersome steps to obtain α,α,α-trisubstituted ester derivatives, it is difficult to effectively realize the "cutting and stitching"...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/343C07D207/337C07D307/54C07D333/24C07F17/02C07C69/738
CPCC07C67/343C07D307/54C07D333/24C07D207/337C07F17/02C07C69/738Y02P20/55
Inventor 程国林巴聃
Owner HUAQIAO UNIVERSITY