biostudies-literatureYu WLNational Natural Science Foundation of China7947-7954https://www.ebi.ac.uk/biostudies/studies/S-EPMC9258329biostudies-literatureUnknown13(26)The transformations that allow the direct removal of hydrogen from their corresponding saturated counterparts by the dehydrogenative strategy are a dream reaction that has remained largely underexplored. In this report, a straightforward and robust cobaloxime-catalyzed photochemical dehydrogenation strategy <i>via</i> intramolecular HAT is described for the first time. The reaction proceeds through an intramolecular radical translocation followed by the cobalt assisted dehydrogenation without needing any other external photosensitizers, noble-metals or oxidants. With this approach, a series of valuable unsaturated compounds such as α,β-unsaturated amides, enamides and allylic and homoallylic sulfonamides were obtained in moderate to excellent yields with good chemo- and regioselectivities, and the synthetic versatility was demonstrated by a range of transformations. And mechanistic studies of the method are discussed.Chemical scienceCobalt-catalyzed chemoselective dehydrogenation through radical translocation under visible light.PMC9258329216320032187111622071085Ma KXYang JJYu WLZheng HXu PFYang HQWu WRen ZGfalseCobalt-catalyzed chemoselective dehydrogenation through radical translocation under visible light.The transformations that allow the direct removal of hydrogen from their corresponding saturated counterparts by the dehydrogenative strategy are a dream reaction that has remained largely underexplored. In this report, a straightforward and robust cobaloxime-catalyzed photochemical dehydrogenation strategy <i>via</i> intramolecular HAT is described for the first time. The reaction proceeds through an intramolecular radical translocation followed by the cobalt assisted dehydrogenation without needing any other external photosensitizers, noble-metals or oxidants. With this approach, a series of valuable unsaturated compounds such as α,β-unsaturated amides, enamides and allylic and homoallylic sulfonamides were obtained in moderate to excellent yields with good chemo- and regioselectivities, and the synthetic versatility was demonstrated by a range of transformations. And mechanistic studies of the method are discussed.2022-01-01T00:00:00Z2022 Jul2025-04-05T14:24:48.815Z2025-04-05T14:24:48.815ZS-EPMC92583293586590610.1039/d2sc02291e