Direct Carbon–Carbon σ Bond Amination of Unstrained Arylalkylketones

Described herein
is the development of an unprecedented approach
to direct amination of unstrained aryl-ketone Csp2–Csp2 sigma bonds with sulfonylazides via Rh­(III)-catalyzed Csp2–Csp2 cleavage. This methodology provides
an efficient strategy for acyl groups/amino groups switch at the C2-position
of indoles in a straightforward fashion. The combination of experimental
and computational studies indicates that beta-aryl elimination derived
from enole-based cyclorhodiumates is a key step, while the formation
of rhodum nitrene is the rate-limiting process.