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 Csp 2 –Csp 2 sigma bonds with sulfonylazides via Rh(III)-catalyzed Csp 2 –Csp 2 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.