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Notably, exploiting a new reaction mode by circumventing the overwhelming cobalt-mediated hydrogen atom transfer would remarkably extend the chemical space of orthogonality-driven functionalization of alkenes. We herein report a cobalt\/photocatalytic carboheterocyclization of unactivated olefins through orchestrating radical addition\/intramolecular radical polarity cross-coupling nucleophilic cyclization. This protocol provides a straightforward route to rapidly assemble a series of saturated heterocycles, such as tetrahydrofuran, tetrahydropyran, tetrahydropyrrole, and piperidine. The designed binary system successfully synchronized the photoinduced radical-involved reaction events with cobalt-mediated polar cross-coupling via high-valent alkylcobalt catalytic species.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03053","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T06:01:59Z","timestamp":1785909719000},"page":"10409-10414","source":"Crossref","is-referenced-by-count":0,"title":["Photoinduced\nCobalt-Catalyzed Alkyl Radical-Initiated\nPolarity Cross-Coupling Cyclization of Unactivated Olefins to Access\nSaturated Heterocycles"],"prefix":"10.1021","volume":"28","author":[{"given":"Keyi","family":"Deng","sequence":"first","affiliation":[{"name":"Central South University , , ,","place":["Changsha, P. R. 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