Iridium-Catalyzed Direct C–H Amination with Alkylamines: Facile Oxidative Insertion of Amino Group into Iridacycle

Described
herein is the development of Cp*Ir­(III)-catalyzed direct
arene C–H amination using alkylamines as an amino source. This
C–N bond formation showcases a notable example of cross-dehydrogenative
coupling to install an amino functionality at the ortho-position of benzamide substrates. Mechanistic studies
including the isolation of an amine-bound iridacyclic intermediate
along with a set of chemical oxidations demonstrated the Ir-catalyzed
inner-sphere C–H amination with primary alkylamines for the first time.