A Metal-Free Oxidative Azidation Method for Selective Azidation of C(sp³)-H Bonds and Diazidation of Alkenes

Current metal-free methods for the synthesis of alkyl (1,2-di)azides mainly rely on highly reactive hypervalent iodine reagents and electrochemical methods, which require specialized electrochemical devices. Herein, we show a robust Selectfluor-promoted oxidative azidation method, which can effectively achieve the selective azidation of C(sp³)-H bonds in alkanes/methylarenes and the diazidation of alkenes, without involving any metal catalyst and additive. The utility of this method is highlighted by the broad substrate scope, late-stage functionalization, and gram-scale synthesis. Mechanistic studies indicate that the reaction proceeds via a radical process.