Temporary Molybdenum η⁶-Coordination Enables Selective and General Dearomative 1,2-Hydrofunctionalization of Benzenes

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 η6-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.