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Enantioselective, Stereoconvergent Resolution Copolymerization of Racemic cis ‐Internal Epoxides and Anhydrides
Author(s) -
He GuangHui,
Ren BaiHao,
Chen ShiYu,
Liu Ye,
Lu XiaoBing
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011259
Subject(s) - kinetic resolution , enantioselective synthesis , enantiopure drug , copolymer , stereocenter , epoxide , chirality (physics) , epoxide hydrolase , ligand (biochemistry) , chemistry , polymer chemistry , stereochemistry , organic chemistry , materials science , catalysis , polymer , biochemistry , chiral symmetry breaking , physics , receptor , microsome , quantum mechanics , quark , nambu–jona lasinio model , enzyme
Unprecedented enantioselective resolution copolymerization of racemic cis‐internal epoxides and anhydrides was mediated by dinuclear aluminum complexes with multiple chirality, affording optically active polyesters with two contiguous stereogenic centers, and the unreacted substrates in good enantioselectivity. Unexpected stereoconvergence is observed in this resolution copolymerization, where the selectivity factor for the enantioselective formation of copolymer significantly exceeds the kinetic resolution coefficient based on the unreacted epoxide at various conversions. Catalytic activity and copolymer enantioselectivity are strongly influenced by the phenolate ortho‐substituents of the ligand set, as well as the axial linker and its chirality. An enantiopure binaphthol‐linked bimetallic Al III complex allows stereoconvergent access to the stereoregular semi‐crystalline polyesters and a concomitant kinetic resolution of the epoxide substrates.