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《科学》 2026年10月8日 · 中文解读

利用氧气活化的不对称酶促膦氢化反应

Asymmetric enzymatic hydrophosphorylation through O2 activation · Y. Zhou et al.
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这篇讲什么
美国伊利诺伊大学的研究团队通过定向进化改造黄素依赖型烯还原酶OYE1,使其利用分子氧产生活性氧物种,进而生成磷中心自由基,实现烯烃与P–H化合物的高对映选择性C–P键构建。最优变体在空气和蓝光下可达到76%产率和98%对映体过量,并适用于亚磷酸酯、亚磷酸及次膦酸等多种底物。该策略还能一步合成草铵膦等有价值的有机磷化合物,为生物催化中利用而非抑制活性氧开辟了新途径。
原文开头
Yi Zhou, Yifei Ge, Wesley Harrison, Huimin Zhao* INTRODUCTION: Carbon–phosphorus (C–P) compounds are widely used in medicines, agriculture, and advanced materials. However, enzymatic C–P bond formation in nature is extremely rare. Chemical methods can construct these bonds through P- centered radicals but often require harsh oxidants or specially activated starting materials and provide limited selectivity. Enzymes could overcome these limitations by guiding highly reactive radical intermediates with precision. A biocatalytic method that directly incorporates common P compounds to alkenes would therefore provide a mild and selective route to value- added, structurally diverse products. RATIONALE: Molecular oxygen (O2) is an attractive, abundant oxidant, but its partial reduction generates reactive oxygen species (ROS) that usually damage enzymes and disrupt radical reactions. …
摘自《科学》(Science)2026年10月8日,Y. Zhou et al.。仅引用开头一小段供了解文章,版权归原刊所有,全文请阅读原刊。
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