Yu Jinhai, Chen Bin, Huang Xiaoqiang
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), ChemBioMed Interdisciplinary Research Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202419262. doi: 10.1002/anie.202419262. Epub 2024 Dec 9.
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.
通过将酶催化与光催化相结合，光酶催化成为一种强大的策略，可增强酶的催化能力，并在涉及反应中间体的反应中提供卓越的立体控制。利用可见光对天然存在的酶进行重新利用是光酶催化最活跃的方向之一。本综述聚焦于该方向的一项前沿策略，即光激发酶催化的单电子氧化引发的非天然生物转化。这些直接的转化具有由单电子氧化引发的独特自由基机制，实现了氧化还原中性的非天然碳-碳、碳-氧和碳-硫键形成，并扩展了酶的化学工具箱。通过突出该领域的最新进展并强调其催化机制和合成潜力，有望为光生物制造带来创新方法。
