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Updated: Feb 16, 2026

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Enantioselective Desymmetrization of Methylenedianilines via Enzyme-Catalyzed Remote Halogenation
James T Payne1, Paul H Butkovich1, Yifan Gu1
1Department of Chemistry, University of Chicago , 5735 South Ellis Avenue, Chicago, Illinois 60637, United States.
Abstract:
Extensive effort has been devoted to engineering flavin-dependent halogenases (FDHs) with improved stability, expanded substrate scope, and altered regioselectivity. Here, we show that variants of rebeccamycin halogenase (RebH) catalyze enantioselective desymmetrization of methylenedianilines via halogenation of these substrates distal to their pro-stereogenic center. Structure-guided engineering was used to increase the conversion and selectivity of these reactions, and the synthetic utility of the halogenated products was shown via conversion of to a chiral α-substituted indole. These results constitute the first reported examples of asymmetric catalysis by FDHs.
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