Single‐Electron Oxidation Triggered by Visible‐Light‐Excited Enzymes for Asymmetric Biocatalysis

By integrating enzymatic catalysis with photocatalysis, photoenzymatic catalysis emerges as a powerful strategy to enhance enzyme catalytic capabilities and provide superior stereocontrol in reactions involving reactive intermediates. Repurposing naturally occurring enzymes using visible light is among the most active directions of photoenzymatic catalysis. This Minireview focuses on a cutting‐edge strategy in this direction, namely single‐electron‐oxidation triggered non‐natural biotransformations catalyzed by photoexcited enzymes. These straightforward transformations feature a unique radical mechanism initiated by single‐electron‐oxidation, achieving redox‐neutral non‐natural C‐C, C‐O, and C‐S bond formations, and expanding the chemical toolbox of enzymes. By highlighting recent advances in this field and emphasizing their catalytic mechanisms and synthetic potentials, innovative approaches for further photobiomanufacturing are anticipated.