Electrochemical Cobalt/Vanadium Relay Catalysis: Enantioselective Markovnikov Hydrooxygenation of Alkenes

ABSTRACT The direct enantioselective intermolecular Markovnikov hydrooxygenation of alkenes remains a fundamental challenge, as it requires simultaneous control over regioselectivity, stereochemistry, and reactivity. Here we report an electrochemical cobalt/vanadium relay catalytic strategy that overcomes these constraints by decoupling regio‐ and stereochemical control across two distinct catalytic events. A cobalt hydride selectively engages alkenes through metal–hydride hydrogen atom transfer to generate a Markovnikov alkyl radical, while a vanadium catalyst mediates a subsequent stereodetermining bimolecular homolytic substitution (S H 2) to form the C─O bond with high enantioselectivity. Electrochemical modulation of the cobalt and vanadium redox states enables efficient catalytic relay under mild conditions, suppressing overoxidation pathways and eliminating the need for stoichiometric chemical oxidants. This approach provides access to a broad range of enantioenriched alcohols and derivatives with high functional group tolerance and scalability, offering streamlined access to pharmaceutically relevant scaffolds. More broadly, the demonstrated compatibility of vanadium‐catalyzed asymmetric bond formation with electrochemical control establishes a general framework for stereoselective C─O bond construction via radical intermediates.