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Method for preparing alpha,beta-unsaturated carboxylate derivatives through visible light catalysis

A technology of derivatives and carboxylic acid esters, which is applied in the field of preparation of α, β-unsaturated carboxylic acid ester derivatives, and can solve the problem of inability to use heterocyclic or aliphatic compounds, limitations, and inability to obtain Z-structure products well etc. to achieve good yield, high selectivity and mild reaction conditions

Inactive Publication Date: 2018-07-13
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

For example, Thomas (Chem. Eur. J. 2009, 15, 4710-4715) et al. reported starting from the Baylis-Hillman addition product and reacting with aryl boronic acid or potassium aryl trifluoroborate under the catalysis of rhodium, The yield is good, but the Z-structure product cannot be obtained well
Rao (Tetrahedron, 2010, 66, 3623-3632) et al. synthesized a series of α, β-unsaturated carboxylate derivatives through palladium-catalyzed substitution reaction of halogenated Baylis-Hillman addition products with triarylbismuth. But the raw material is limited to triaryl bismuth, and heterocyclic or aliphatic compounds cannot be used

Method used

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  • Method for preparing alpha,beta-unsaturated carboxylate derivatives through visible light catalysis
  • Method for preparing alpha,beta-unsaturated carboxylate derivatives through visible light catalysis
  • Method for preparing alpha,beta-unsaturated carboxylate derivatives through visible light catalysis

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] In a Schlenk tube, add methyl 2-((tert-butoxycarbonyloxy)(phenyl)methyl)acrylate (292.3 mg, 1 mmol), potassium benzyltrifluoroborate (396.0 mg, 2 mmol), Ir [dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (11.2mg, 0.01mmol) and N-methylpyrrolidone (4mL), connected to a nitrogen atmosphere, stirred at room temperature for 25h under the irradiation of a 45W energy-saving lamp white light. After the reaction was completed, the resulting reaction solution was washed with 25 mL of distilled water, extracted three times with 30 mL of ether, the combined organic phase was separated by silica gel column chromatography, and the eluent containing the target product was collected using PE / EA (20 / 1) as the eluent. The light yellow target product 2-benzylidene-4-phenylbutyric acid methyl ester was isolated with a yield of 73.61%. The product characterization data are as follows: 1H NMR (500MHz, CDCl3) δ7.76(s,1H),7.41–7.21(m,26.29H),6.60(s,1.26H),3.86(s,3H),3.68(s, 3.81H),2.90–2.87(m,6.80H),2.76–2...

Embodiment 2

[0038] In a Schlenk tube, add methyl 2-((tert-butoxycarbonyloxy)(phenyl)methyl)acrylate (292.3 mg, 1 mmol), potassium benzyltrifluoroborate (396.0 mg, 2 mmol), Ir [dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (11.2mg, 0.01mmol) and dimethyl sulfoxide (4mL), connected to a nitrogen atmosphere, and stirred at room temperature for 25h under the irradiation of a 45W energy-saving lamp white light. After the reaction was completed, the resulting reaction solution was washed with 25 mL of distilled water, extracted three times with 30 mL of ether, the combined organic phase was separated by silica gel column chromatography, and the eluent containing the target product was collected using PE / EA (20 / 1) as the eluent. The light yellow target product 2-benzylidene-4-phenylbutyric acid methyl ester was isolated with a yield of 51.86%.

Embodiment 3

[0040] In a Schlenk tube, add methyl 2-((tert-butoxycarbonyloxy)(phenyl)methyl)acrylate (292.3 mg, 1 mmol), potassium benzyltrifluoroborate (396.0 mg, 2 mmol), Ir [dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (11.2mg, 0.01mmol) and 1,2-dichloroethane (4mL), connected to a nitrogen atmosphere, and stirred at room temperature for 25h under the irradiation of a 45W energy-saving lamp white light. After the reaction was completed, the resulting reaction solution was washed with 25 mL of distilled water, extracted three times with 30 mL of ether, the combined organic phase was separated by silica gel column chromatography, and the eluent containing the target product was collected using PE / EA (20 / 1) as the eluent. The light yellow target product 2-benzylidene-4-phenylbutyric acid methyl ester was isolated with a yield of 55.36%.

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Abstract

The invention provides a method for preparing alpha,beta-unsaturated carboxylate derivatives by using Baylis-Hillman derivatives and organic potassium trifluoroborate through visible light catalysis.The method comprises the following steps of adding the Baylis-Hillman derivatives shown in a formula (I), organic potassium trifluoroborate shown in a formula (II) and a light catalyst into an organicsolvent; stirring for 15 to 30h under the nitrogen atmosphere and visible light radiation condition at normal temperature and normal pressure; post-treating a reaction solution, so as to obtain the alpha,beta-unsaturated carboxylate derivative shown in the formula (I). The preparation method has the advantages that the reaction conditions are mild, the operation is simple, and the yield rate is high; by adopting the visible light catalysis, the pollution is avoided, the environment-friendly effect is realized, and the like; the method has prospect. (The formulas are shown in the attached figures.).

Description

(1) Technical field [0001] Visible light has the characteristics of green, pollution-free and easy to obtain. The invention relates to a method for preparing alpha, beta-unsaturated carboxylate derivatives by utilizing visible light catalysis. The method has the advantages of simple and convenient reaction conditions, convenient operation, good reaction regioselectivity, and easy regulation of substituents. (2) Background technology [0002] α,β-Unsaturated carboxylic acid ester derivatives are an important class of organic synthesis intermediates, which are of great significance in organic synthesis, and many important compounds can be synthesized through chemical transformation. For example, α,β-unsaturated carboxylic acids are important intermediates for the preparation of pharmacologically active substances such as calcium antagonists or pesticides, and optically active acids can also be prepared by asymmetric hydrogenation. α, β-unsaturated carboxylic acid hydroxyalky...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/618C07C69/734C07C67/30C07D307/54C07D333/24C07D213/55
CPCC07C67/30C07D213/55C07D307/54C07D333/24C07C69/618C07C69/734
Inventor 许孝良叶弘强叶倩雯张群峰马磊卢春山丰枫李小年
Owner ZHEJIANG UNIV OF TECH