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Stereoselective Organic Reactions in Aggregate Catalytic Systems and Their Application to Functional Materials

聚集体催化体系中的立体选择性有机反应及其在功能材料中的应用

基本信息

批准号：
62550639
负责人：
IHARA Yasuji
金额：
$ 1.28万
依托单位：
Yamaguchi Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

In order to gain the basic information about the mechanisms on the stereoselective organic reactions, the hydrolysis of amino acid esters by optically active catalysts were investigated in various aggregate domains.The following results were obtained; 1) In the hydrolysis of the enantiomers by catalytic domains composed of catalytic surfactant aggregates and catalysts, the dipeptide catalysts showed large rate enhancement and stereoselectivity. The surfactant structural effects were discussed by investigation on the rate constants and stereoselectivities. 2) The rate constants of both acylation and deacylation in the hydrolysis of esters catalyzed by optically active catalysts have been determined in the presence of surfactant micelles. Micellar catalysis in deacylation as well as acylation was discussed in terms of the rate constants and stereoselectivity. 3) Stereoselective hydrolysis of chiral esters was examined in branched or linear poly(ethylenimine) derivatives covalently linked dipeptede -containing histidine. The effect of the ester structure influenced both the rate constant and stereoselectivity in the hydrolysis by poly(ethylenimine) derivatives. 4) The stereoselective hydrolysis of the esters has been found to be easily controlled by changing the composition of the aggregates. Especially noteworthy is the fact that the high stereoselectivity was obtained in coaggregates of optically active surfactant micelles and bilayer membranes.

为了了解立体选择性有机反应机理的基本信息，我们在不同的聚集体领域对光学活性催化剂催化氨基酸酯的反应进行了研究，得到以下结果：1)在由表面活性剂聚集体和催化剂组成的催化域催化体系中，二肽催化剂表现出较大的速率提高和立体选择性。通过对反应速率常数和立体选择性的研究，讨论了表面活性剂的结构效应。2)测定了在表面活性剂胶束存在下，光学活性催化剂催化酯类的酰化反应和脱酰反应的速率常数。从速度常数和立体选择性两个方面讨论了胶束催化脱酰化和酰化反应。3)研究了含二肽组氨酸的支链或线形聚乙二亚胺衍生物中手性酯的立体选择性水解性。酯结构的影响对聚乙二亚胺衍生物的反应速率常数和立体选择性都有影响。4)通过改变聚集体的组成，可以很容易地控制酯的立体选择性水解。特别值得注意的是，在光学活性表面活性剂胶束和双层膜的共聚体中获得了高的立体选择性。