Using α,α-difluoromethylene alkyne as a nontraditional one-carbon reaction partner, a synthetically novel method for the construction of isoindolin-1-one derivatives via Rh(III)-catalyzed [4+1] annulation reaction is reported. The 2-fold C-F bond cleavage not only enables the generation of desired product under an overall oxidant-free condition but also results in a net migration of carbon-carbon triple bond. In addition, the present reaction protocol exhibits a tolerance of a wide spectrum of functional groups due to the mild reaction conditions employed.

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.

A novel and efficient copper-catalyzed oxyazidation and diazidation of styrenes is described. The stable azidoiodine(III) reagent is used as an efficient azide radical source in this reaction. A variety of synthetically useful functional groups are compatible with the mild reaction conditions. This protocol enables the straightforward synthesis of various functionalized azides in good-to-excellent yields.