α‐Nucleophilic Addition to α,β‐Unsaturated Carbonyl Compounds via Photocatalytically Generated α‐Carbonyl Carbocations

Abstract We report the photocatalytic oxidation of α‐carbonyl radicals of amides or esters to the corresponding α‐carbonyl carbocations through super photoreductant CBZ6 induced redox‐neutral photocatalysis. The α‐carbonyl radicals are formed by the β‐addition of alkyl radicals generated in situ by the photocatalytic fragmentation of N ‐hydroxyphthalimide esters to the α,β‐unsaturated amides and esters. This method enables the α‐nucleophilic addition of hydroxyl or alkoxyl radicals to amides and esters without any prefunctionalization.