Empowering Precision C–H Functionalization: Advances in Peroxygenase Engineering
Angewandte Chemie International Edition, vol. 65, pp. e25086
Abstract
Abstract Selective C–H functionalization remains a central challenge in modern synthesis as it enables direct diversification of molecular scaffolds without pre‐functionalization. Peroxygenases, including both unspecific peroxygenases and P450 peroxygenases, offer a biocatalytic solution to this challenge, catalyzing oxyfunctionalization reactions in aqueous media under mild conditions with hydrogen peroxide (H 2 O 2 ) as the sole oxidant. In this review, we highlight recent advances in peroxygenase engineering over the past five years, with a particular focus on strategies that enhance heterologous expression, catalytic activity, and control of regio‐ and enantioselectivity. We also discuss protein engineering approaches that mitigate H 2 O 2 ‐induced inactivation and summarize efforts to repurpose NADPH‐dependent P450 enzymes into self‐sufficient peroxygenases, thereby expanding their catalytic repertoire. Furthermore, we examine the integration of peroxygenases with in situ H 2 O 2 generation systems by enzymatic, chemical, photocatalytic, and electrochemical methods to achieve balanced oxidant delivery and sustained turnover. Collectively, these developments have established peroxygenases as versatile and robust catalysts for selective C–H functionalization, opening new opportunities for their application in the synthesis of pharmaceuticals, fine chemicals, and agrochemicals.
Authors 8
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Affiliation as printed
Ministry of Education Key Laboratory of NSLSCS Nanjing Normal University Nanjing 210097 China
State Key Laboratory of Microbial Technology College of Life Sciences Nanjing Normal University Nanjing 210097 China
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Affiliation as printed
Institute of Biotechnology RWTH Aachen University Aachen 52074 Germany
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Affiliation as printed
CSPC Pharmaceutical Group Limited Shijiazhuang 050035 China
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Affiliation as printed
Ministry of Education Key Laboratory of NSLSCS Nanjing Normal University Nanjing 210097 China
State Key Laboratory of Microbial Technology College of Life Sciences Nanjing Normal University Nanjing 210097 China
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Nanjing Tech University · State Key Laboratory of Materials-Oriented Chemical Engineering
Affiliation as printed
State Key Laboratory of Materials‐Oriented Chemical Engineering School of Pharmaceutical Sciences Nanjing Tech University Nanjing 210009 China
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Zhejiang University of Technology
Affiliation as printed
College of Biotechnology and Bioengineering Zhejiang University of Technology Hangzhou 310014 China
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Xiaofei Song corresponding
Zhejiang University of Technology
Affiliation as printed
College of Biotechnology and Bioengineering Zhejiang University of Technology Hangzhou 310014 China
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Haiyang Cui corresponding
Affiliation as printed
Ministry of Education Key Laboratory of NSLSCS Nanjing Normal University Nanjing 210097 China
State Key Laboratory of Microbial Technology College of Life Sciences Nanjing Normal University Nanjing 210097 China
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