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

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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.