Gold-catalyzed azidation with TMSN3 and mechanistic studies

Abstract

The growing demand for aryl azides in diverse fields has spurred significant advances in their synthetic methodologies. Herein, we report a gold-catalyzed C–N₃ cross-coupling reaction enabled by ligand-supported Au(I)/Au(III) redox catalysis. This method employs trimethylsilyl azide (TMSN₃) as a practical azide source to efficiently convert simple aryl iodides into the corresponding aryl azides. Key features of this transformation include broad substrate scope and compatibility with post-functionalization strategies. Mechanistic insights derived from combined experimental studies, computational analyses, and X-ray crystallography of two key intermediates reveal that oxidative addition and ligand exchange/azide transfer proceed smoothly, whereas thermal or photoinduced conditions facilitate the challenging reductive elimination of the Au(III)–azide intermediate.