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However, these transformations typically require the use of oxygen\u2010protected oximes, and a general strategy to directly utilize free oximes remains challenging due to their vulnerability to side reaction pathways, rendering low tendency towards N\u2500OH bond cleavage. Here a unified platform is reported to achieve direct cyclization of unprotected oximes with enals, as well as other coupling partners through dual copper\/organophotoredox catalysis under green light irradiation. This protocol enables concurrent activation of both N\u2500OH and <jats:italic>\u03b1<\/jats:italic>\u2010C(sp<jats:sup>3<\/jats:sup>)\u2500H bonds of free oximes to form multisubstituted pyridines with exceeding structural diversity and functional group tolerance. In this process, Rose Bengal serves as a hydrogen atom transfer agent to generate radical intermediates. In the meanwhile, copper catalyst activates of free oximes via single\u2010electron reduction\u2010induced N\u2500O bond fragmentation and controls the selectivity for intermediate trapping. The synthetic utility of this approach is further demonstrated by its successful applications in late\u2010stage modification of biologically active compounds and rapid assembly of solvatochromic fluorescent materials.<\/jats:p>","DOI":"10.1002\/anie.202501806","type":"journal-article","created":{"date-parts":[[2025,3,11]],"date-time":"2025-03-11T17:50:12Z","timestamp":1741715412000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Unlocking Reactivity of Unprotected Oximes via Green\u2010Light\u2010Driven Dual Copper\/Organophotoredox Catalysis"],"prefix":"10.1002","volume":"64","author":[{"given":"Shuping","family":"Wang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian 350002 P.R. 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