Transaminase-catalyzed sequential hydrodefluorinations of perfluorinated methylene groups

作者：Xiaoyang Chen, Yuting Zhang, Jiajie Fu, Ziyi Chen, Xinyi Zhou, Xiaohe Chu · 发表于：Communications Chemistry · 年份：2025 · DOI：10.1038/s42004-025-01781-y · 被引用次数：1 · 研究领域：Fluorine in Organic Chemistry、Per- and polyfluoroalkyl substances research、Cyclopropane Reaction Mechanisms

Biocatalysis represents a particularly promising approach for the degradation of recalcitrant fluorochemicals. However, the enzymatic activation of perfluorinated methylene groups remains a challenge, primarily due to the increase in C–F bond strength that correlates with the number of fluorine atoms attached to a single carbon atom. Here, we describe a new-to-nature hydrodefluorination reaction catalyzed by engineered transaminases for the biodegradation of difluorinated fused-ring ketones. Remarkable defluorination efficiency was achieved in most cases by employing a slight excess of 2-PrNH2 as amine donor. Experimental results provide conclusive evidence that the catalytic process commences with a reversible transamination step. The comprehensive examination of this promiscuous reaction provides constructive guidance for the development of emerging biocatalytic strategies, thereby facilitating the biodegradation of polyfluorinated compounds and contributing to environmental sustainability. Fluorochemicals pose significant environmental challenges due to their persistence and strong C–F bonds. Here, the authors engineer transaminases to catalyze a hydrodefluorination reaction of perfluorinated methylene groups, achieving efficient biodegradation of difluorinated ketones.