Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer

A bicyclic olefin was discovered as a cocatalyst in a Cp*Rh­(III)-catalyzed C–H bond amidation proceeding by an intramolecular amide transfer in <i>N</i>-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh­(III) intermediate to undergo oxidative addition into the O–N bond to form a Rh­(V) nitrenoid species and subsequently direct the nitrenoid to add to the <i>ortho</i> position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C–H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.