Oxidative Rearrangement of Primary Amines Using PhI(OAc)2 and Cs2CO3.

An oxidative rearrangement of primary amines mediated by a hypervalent iodine(III) reagent is herein reported. The combination of PhI(OAc)2 and Cs2CO3 proves highly efficient at inducing the direct 1,2-C to N migration of primary amines, which can be applied to the preparation of both acyclic and cyclic amines. A mechanistic study shows that the rearrangement proceeds via a concerted mechanism.