Manganese-Catalyzed Oxidative Azidation of Cyclobutanols: Regiospecific Synthesis of Alkyl Azides by CC Bond Cleavage

A novel, manganese‐catalyzed oxidative azidation of cyclobutanols is described. A wide range of primary, secondary, and tertiary alkyl azides were generated in synthetically useful yields and exclusive regioselectivity. Aside from linear alkyl azides, otherwise elusive medium‐sized cyclic azides were also readily prepared. Preliminary mechanistic studies reveal that the reaction likely proceeds by a radical‐mediated CC bond cleavage/CN3 bond formation pathway. Cleaved: An efficient manganese‐catalyzed synthesis of alkyl azides is based on the CC bond cleavage of cyclobutanols. A wide range of primary, secondary, and tertiary alkyl azides and a series of medium‐sized cyclic azides were generated in synthetically useful yields. Preliminary mechanistic studies suggest that the reaction proceeds by a radical mechanism.