Fluorine Effects on Group Migration via a Rhodium(V) Nitrenoid Intermediate

An unprecedented rhodium(III)-catalyzed hydroarylation of α,α-difluoromethylene alkynes with N-pivaloxyl aroylamides through sequential C−H activation and aryl migration is detailed herein. A large array of α,α-difluoromethylene alkynes and N-pivaloxyl aryl amides were amenable to this transformation, thus providing a novel synthetic protocol for the construction of difluorinated 2-alkenyl aniline derivatives in high yields and with excellent regioselectivity. Notably, unique fluorine effects were found to underlie the thus unconventional reaction manifold.