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Significance The accurate control of macromolecular stereochemistry and sequences is a powerful strategy to manipulate polymer properties. The enantioselective terpolymerization of anhydrides with two kinds of substituted epoxides exhibiting different reactivities and stereogenic centers offers the accessibility to stereochemistry- and sequence-defined polymers. In this paper, we utilize the privileged chiral dinuclear Al(III) catalyst for the enantioselective terpolymerization of cyclic anhydrides, racemic epoxides, andmeso -epoxides, to prepare optically active terpolyesters with gradient or random distributions. In particular, the crystallization behaviors of the resultant gradient terpolyesters vary 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.

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