Enantioselective terpolymerization of racemic and meso-epoxides with anhydrides for preparation of chiral polyesters

Abstract

The preparation of stereochemistry- and sequence-defined polymers, in which different monomer units are arranged in an ordered fashion just like biopolymers, is of great interest and has been a long-standing goal for chemists due to the expectation of unique macroscopic properties. Here, we describe the enantioselective terpolymerization of racemic terminal epoxides, meso-epoxides, and anhydrides mediated by the privileged chiral dinuclear Al(III) catalyst system, to afford optically active polyester terpolymers with either gradient or random distribution as determined by the epoxides employed during their preparation. The enantioselective terpolymerization of racemic tert-butyl glycidyl ether (rac-TBGE) and cyclopentene oxide with phthalic anhydride (PA) or naphthyl anhydride (NA) gives novel gradient polyesters, in which the crystallization behavior varies continuously along the main chain, due to the decrement of one ester component and the increment of the other occurring sequentially from one chain end to the other. In contrast, the enantioselective terpolymerization of rac-TBGE and meso-epoxide (cyclohexene oxide, 3,4-epoxytetrahydrofuran, or 1,4-dihydronaphthalene oxide) with an anhydride (PA or NA) provided chiral statistical terpolyesters with the random distribution of two kinds of ester units, resulting in a material possessing a mixed glass transition temperature. The present study therefore provides a convenient route to chiral polyesters bearing a range of physical and degradability properties.