Amines as Dual‐Function Reagents in Photoredox‐Mediated Synthesis of α‐Ketoamide via C─N Bond Cleavage

A mild photoredox‐catalyzed method for the C─N bond cleavage of aliphatic tertiary amines to construct medicinally significant α‐ketoamides has been reported. The reaction showcases the simultaneous formation of C─N and C─O bonds in a single step. In this study, the tertiary amine acts as a dual‐function reagent, serving both as a reductant and nitrogen source, thereby obviating the need for external nitrogen‐based coupling partners in the presence of phenylacetylene and catalytic thiophenol. Beyond providing an easier route to complex molecules from simple starting materials, our work highlights the hidden utility of tertiary amines in photoredox catalysis, offering a platform for late‐stage functionalization and C─N bond activation.