Temporary Molybdenum η 6 -Coordination Enables Selective and General Dearomative 1,2-Hydrofunctionalization of Benzenes

作者：Jia‐Yi Qiu, Jun-Jie Zhi, Qin He, Mingyang Wang, Wei‐Long Zeng, Chuqiao Li, Wei Li · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c15942 · 被引用次数：8 · 研究领域：Catalytic C–H Functionalization Methods、Asymmetric Hydrogenation and Catalysis、Synthetic Organic Chemistry Methods

Despite molybdenum’s sustainable profile and broad utility in organic synthesis, its use in high-value arene dearomative functionalizations remains markedly underexplored. Herein, we report a general and efficient dearomative 1,2-hydrofunctionalization of nonactivated arenes via transient molybdenum η 6 -coordination. This method operates under mild conditions and exhibits broad substrate scope and high regioselectivity, thus providing convenient access to valuable functionalized 1,3-cyclohexadienes. The molybdenum activation allows precise ring-selective dearomatization within complex polyaromatic systems and facilitates late-stage modification of drug molecules. Its synthetic utility is further demonstrated through the total synthesis of (±)-infectocaryone and formal syntheses of (±)-juvabione and (±)-lycorane. Notably, the molybdenum-based system demonstrates unique reactivity and superior selectivity compared to conventional chromium analogues, highlighting its distinct capability for selective dearomative functionalization.