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Despite significant advances in the field, the coupling of aliphatic carbonyls with unsaturated molecules remains a critical challenge. Herein, we present how a novel catalytic activation mode for aliphatic carbonyl compounds enables the development of a mild and general platform for reductive couplings. Central to this process is the formation of a hemiaminal intermediate with a nucleophilic phenothiazine catalyst, which releases alkyl ketyl radicals via photolysis upon absorption of visible light. 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