Catalytic Enantioselective Synthesis of Phosphonamidates from Racemic Phosphonamidites Using Anionic Stereogenic-at-Cobalt(III) Complexes

作者：Zu‐Kui Xie, Zhiyuan Pan, Y Cui, Hua‐Jie Jiang, Meng‐Lan Shen, Chuan‐Zhi Yao, Qiankun Li, Jie Yu · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c04951 · 被引用次数：9 · 研究领域：Organophosphorus compounds synthesis、Asymmetric Hydrogenation and Catalysis、Asymmetric Synthesis and Catalysis

Catalytic asymmetric oxidation of racemic P(III) species remains largely unexplored and represents a significant challenge compared with the well-established S - or N -oxidation reactions. Herein, we exhibit an efficient bromophosphonium ion-promoted enantioselective synthesis of phosphonamidates from racemic phosphonamidites. By using anionic stereogenic-at-cobalt(III) complexes as catalysts, a variety of chiral phosphonamidates were obtained in high yields with good enantioselectivities (up to 97:3 enantiomeric ratio (er)). Antifungal testing shows these P(V) compounds exhibit broad-spectrum activity, suggesting their potential as fungicides.