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

为了获得立体选择性有机反应机理的基本信息，在不同聚集域上研究了光学活性催化剂对氨基酸酯的水解。得到以下结果：1)在催化表面活性剂聚合体和催化剂组成的催化域水解对映体时，二肽催化剂表现出较大的速率增强和立体选择性。通过对反应速率常数和立体选择性的研究，探讨了表面活性剂的结构效应。2)在表面活性剂胶束存在的情况下，测定了光学活性催化剂催化酯类水解过程中酰化和去酰化的速率常数。从速率常数和立体选择性的角度讨论了脱酰化和酰化反应中的胶束催化。3)研究了支链或线状聚亚胺共价连接二肽组氨酸衍生物的手性酯的立体选择性水解。酯结构对聚亚胺衍生物水解反应的速率常数和立体选择性均有影响。4)酯类化合物的立体选择性水解很容易通过改变聚集体的组成来控制。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共聚集体中获得了高立体选择性。

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.