Ir(III)-Catalyzed Mild C–H Amidation of Arenes and Alkenes: An Efficient Usage of Acyl Azides as the Nitrogen Source

Reported
herein is the development of the Ir­(III)-catalyzed direct
C–H amidation of arenes and alkenes using acyl azides as the
nitrogen source. This procedure utilizes an in situ generated cationic
half-sandwich iridium complex as a catalyst. The reaction takes place
under very mild conditions, and a broad range of sp2 C–H
bonds of chelate group-containing arenes and olefins are smoothly
amidated with acyl azides without the intervention of the Curtius
rearrangement. Significantly, a wide range of reactants of aryl-,
aliphatic-, and olefinic acyl azides were all efficiently amidated
with high functional group tolerance. Using the developed approach, Z-enamides were readily accessed with a complete control
of regio- and stereoselectivity. The developed direct amidation proceeds
in the absence of external oxidants and releases molecular nitrogen
as a single byproduct, thus offering an environmentally benign process
with wide potential applications in organic synthesis and medicinal
chemistry.