A Facile Access to Primary Alkylamines and Anilines via Ir(III)-Catalyzed C–H Amidation Using Azidoformates

Described
herein is the development of Ir­(III)-catalyzed direct
C–H amidation using azidoformates as a readily deprotectable
amino source. Substrates with unactivated methyl C­(sp3)–H
and aromatic or olefinic C­(sp2)–H bonds were smoothly
reacted by the iridium-based catalyst system to provide the corresponding
primary alkylamines and anilines upon the subsequent removal of N-protecting
groups, such as Boc, Fmoc, Cbz, pNZ, or Troc. A brief mechanistic
study and synthetic applications are also presented.