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.

为了获得有关立体选择性有机反应机制的基本信息，研究了在各种聚集域中通过光学活性催化剂对氨基酸酯的水解。获得以下结果。 1）在由由催化表面活性剂聚集体和催化剂组成的催化域对对映体的水解中，二肽催化剂显示出较大的增强率和立体选择性。通过研究速率常数和立体选择性来讨论表面活性剂的结构效应。 2）在存在表面活性剂胶束的情况下，已经确定了光学活性催化剂催化的酯水解中酰化和脱酰化的速率常数。根据速率常数和立体选择性讨论了脱酰化和酰化的胶束催化。 3）在分支或线性聚（乙基亚胺）衍生物共价连接的含二培养基的组氨酸中，检查了手性酯的立体选择性水解。酯结构的作用影响了聚（乙二胺）衍生物水解中的速率常数和立体选择性。 4）发现酯的立体选择性水解可以通过更改聚集体的组成而容易控制。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凝集群中获得了高立体选择性。