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

Abstract 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 formation, and expanding the chemical toolbox of enzymes. By highlighting recent advances in this field and emphasizing their catalytic mechanisms and synthetic potential, innovative approaches for photobiomanufacturing are anticipated.