Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer
2017-04-18T00:00:00Z (GMT) by
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 N-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 ortho 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.