Highly γ‐Selective Arylation and Carbonylative Arylation of 3‐Bromo‐3,3‐difluoropropene via Nickel Catalysis

A nickel‐catalyzed highly γ‐regioselective arylation and carbonylative arylation of 3‐bromo‐3,3‐difluoropropene has been developed. The reaction proceeds under mild reaction conditions, providing the gem‐difluoroalkenes with high efficiency and good functional group tolerance. The resulting gem‐difluoroalkenes can serve as versatile building blocks for diversified synthesis. Preliminary mechanistic studies and density functional theory calculations reveal that both non‐radical and radical pathways are possible for the reaction, and the radical pathway is more likely. The high γ‐regioselectivity results from the β‐bromide elimination of alkylnickel(II) species or from the reductive elimination of nickel(III) species [(aryl)(CF2=CHCH2)NiIII(Ln)X]. The γ‐selective carbonylation of 3‐bromo‐3,3‐difluoropropene under 1 atm CO gas also provides a new way for nickel‐catalyzed carbonylation. A nickel‐catalyzed highly γ‐regioselective arylation and carbonylation of 3‐bromo‐3,3‐difluoropropene has been developed. The reaction provides a variety of gem‐difluoroalkenes with good functional group tolerance and high efficiency. Preliminary mechanistic studies and DFT calculations revealed that both non‐radical and radical pathways are possible for the reaction.