Construction of α‐ketoamides via Photoredox‐Catalyzed N−H Insertion of Amines by Sulfoxonium Ylides

Herein, we report the development of photoredox‐catalyzed N−H insertion of sulfoxonium ylides with amines via oxidative single‐electron transfer (SET). These reactions exhibit broad substrate scope (32 examples) and offer operationally simple, scalable procedures for accessing α‐ketoamides in a single step. Mechanistic studies and control experiments confirm the participation of a photogenerated carbon radical in facilitating the oxidative single‐electron transfer (SET) from the sulfoxonium ylides to initiate the reaction.