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Herein, we report a photometallobiocatalytic enantioselective intermolecular C\u2500C cross\u2010coupling of pyridotriazoles and secondary alkyltrifluoroborate salts through cooperative catalysis between an organic photosensitizer and an engineered protoglobin. By combining visible\u2010light\u2010mediated radical generation with enzymatic activation of pyridotriazoles to form reactive Fe carbenoid intermediates, this transformation enabled highly enantioselective radical C\u2500C bond formation through a proposed outer\u2010sphere coupling mechanism. Through biocatalyst mining and directed evolution, engineered\n                    <jats:italic>Aeropyrum pernix<\/jats:italic>\n                    protoglobin catalysts were developed that catalyzed this radical C\u2013C coupling with excellent efficiency and stereocontrol. The photobiocatalytic platform exhibited a broad substrate scope with respect to both secondary alkyltrifluoroborate salts and pyridotriazoles, affording a range of valuable N\u2010heterocyclic products in excellent yields and enantioselectivities. Mechanistic studies supported the involvement of radical intermediates and revealed spontaneous binding between the photocatalyst eosin B and the engineered metalloenzyme. By leveraging cooperative photometallobiocatalysis, this work established an underexplored strategy for asymmetric intermolecular radical cross\u2010coupling via an outer\u2010sphere mechanism, further expanding the catalytic repertoire of transition\u2010metal carbenoid chemistry.\n                  <\/jats:p>","DOI":"10.1002\/anie.7251439","type":"journal-article","created":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T09:08:50Z","timestamp":1787389730000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Photometallobiocatalytic Asymmetric Radical\u2010Mediated Cross\u2010Coupling of Organotrifluoroborate Salts and Pyridotriazoles"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9699-3358","authenticated-orcid":false,"given":"Huanan","family":"Wang","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  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