Biocatalytic enantioselective formation and ring-opening of oxetanes

Xia Hua, Yuan-Fei Wang, Xiao Jin, Hong-Yin Yu, Hui-Hui Wang, Yong-Zheng Chen and Nan-Wei Wan ()
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Xia Hua: Zunyi Medical University
Yuan-Fei Wang: Zunyi Medical University
Xiao Jin: Zunyi Medical University
Hong-Yin Yu: Zunyi Medical University
Hui-Hui Wang: Zunyi Medical University
Yong-Zheng Chen: Zunyi Medical University
Nan-Wei Wan: Zunyi Medical University

Nature Communications, 2025, vol. 16, issue 1, 1-12

Abstract: Abstract Although biocatalysis offers complementary or alternative approaches to traditional synthetic methods, the limited range of available enzymatic reactions currently poses challenges in synthesizing a diverse array of desired compounds. Consequently, there is a significant demand for developing novel biocatalytic processes to enable reactions that were previously unattainable. Herein, we report the discovery and subsequent protein engineering of a unique halohydrin dehalogenase to develop a biocatalytic platform for enantioselective formation and ring-opening of oxetanes. This biocatalytic platform, exhibiting high efficiency, excellent enantioselectivity, and broad scopes, facilitates the preparative-scale synthesis of chiral oxetanes and a variety of chiral γ-substituted alcohols. Additionally, both the enantioselective oxetane formation and ring-opening processes are proven scalable for large-scale transformations at high substrate concentrations, and can be integrated efficiently in a one-pot, one-catalyst cascade system. This work expands the enzymatic toolbox for non-natural reactions and will promote further exploration of the catalytic repertoire of halohydrin dehalogenases in synthetic and pharmaceutical chemistry.

Date: 2025
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DOI: 10.1038/s41467-025-56463-z

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