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Here we report an electrochemical cobalt\/vanadium relay catalytic strategy that overcomes these constraints by decoupling regio\u2010 and stereochemical control across two distinct catalytic events. A cobalt hydride selectively engages alkenes through metal\u2013hydride hydrogen atom transfer to generate a Markovnikov alkyl radical, while a vanadium catalyst mediates a subsequent stereodetermining bimolecular homolytic substitution (S\n                    <jats:sub>H<\/jats:sub>\n                    2) to form the C\u2500O 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\u2010catalyzed asymmetric bond formation with electrochemical control establishes a general framework for stereoselective C\u2500O bond construction via radical intermediates.\n                  <\/jats:p>","DOI":"10.1002\/anie.1324586","type":"journal-article","created":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T11:12:43Z","timestamp":1788347563000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Electrochemical Cobalt\/Vanadium Relay Catalysis: Enantioselective Markovnikov Hydrooxygenation of Alkenes"],"prefix":"10.1002","volume":"65","author":[{"given":"Pan","family":"Peng","sequence":"first","affiliation":[{"name":"The Institute for Advanced Studies Wuhan University  Wuhan Hubei P.R. 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China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2852-3220","authenticated-orcid":false,"given":"Qingquan","family":"Lu","sequence":"additional","affiliation":[{"name":"The Institute for Advanced Studies Wuhan University  Wuhan Hubei P.R. China"},{"name":"Beijing National Laboratory For Molecular Sciences  Beijing P.R. China"},{"name":"The Key Laboratory of Functional Molecular Solids Ministry of Education Anhui Normal University  Wuhu P.R. 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