Nickel-Catalyzed <i>anti</i>-Markovnikov Hydrodifluoroalkylation of Unactivated Alkenes

An efficient Ni-catalyzed hydrodifluoroalkylation of unactivated alkenes with bromodifluoroacetate by using PhSiH₃ as hydride source was developed. The transformation affords aliphatic difluorides with <i>anti</i>-Markovnikov regioselectivity. A wide range of highly remote alkenes, simple alkenes, drug molecules, commercially available CF₂ precursors, and even nonfluorinated substrates are competent in this reaction under mild conditions, demonstrating the practicability of the strategy. Moreover, mechanistic studies indicated that the difluoroalkyl radical might be a key intermediate to this transformation.