Photoenzymatic enantioselective synthesis of fluorinated amides with remote stereocenter

Abstract Fluorinated compounds are scarce in nature, albeit they are in high demand in pharmaceuticals, agrochemicals, and materials. Fluorinated amides serve as prevalent structural motifs in pharmaceuticals and bioactive molecules. However, enantioselective synthesis of fluorinated amides remains...

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Bibliographic Details
Main Authors: Chaoqun Huang, Xuerui Jin, Zhenyu Liu, Can Cui, Yang Zhang, Binju Wang, Chun Zhang, Jianqiang Feng, Dawen Niu, Yunzi Luo
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-60807-0
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Summary:Abstract Fluorinated compounds are scarce in nature, albeit they are in high demand in pharmaceuticals, agrochemicals, and materials. Fluorinated amides serve as prevalent structural motifs in pharmaceuticals and bioactive molecules. However, enantioselective synthesis of fluorinated amides remains challenging. Herein, we develop a visible-light-driven ene-reductase system that effectively generates carbon-centered radicals from fluorine-containing brominated amides. The system further enables their enantioselective hydroalkylation with alkenes, achieving high stereocontrol. Diversified α-fluorinated amides with high yield (up to 91%) and distal chirality (γ-to F, up to 97% enantiomeric excess) are produced by optimizing the reaction system and performing enzyme engineering. This work advances photoenzymatic strategies for the integration of fluorinated chemical inputs and creates an opportunity for the asymmetric synthesis of valuable fluorinated compounds.
ISSN:2041-1723