Metal-Free C–N or C–C Bond Cleavages of α‑Azido Ketones: An Oxidative-Amidation Strategy for the Synthesis of α‑Ketothioamides and Amides

A novel metal-free oxidative-amidation strategy for the synthesis of α-ketothioamides and amides from α-azido ketones was developed. The C–H bond thionation of α-azido ketones with elemental sulfur could form α-ketothioacyl azide, which was then nucleophilically attacked by amines, causing the cleavage of the C–N bond to afford α-ketothioamides, while amides could be formed with the release of nitrogen gas and cyano anion in the presence of PhI­(OAc)2 by selective C–C bond cleavage.