Oxy-difluoroallylation of Ynamides by Nickel-Catalyzed Tandem Alkoxylation/Claisen Rearrangement

A nickel-catalyzed tandem alkoxylation/claisen rearrangement strategy for the oxy-difluoroallylation of ynamides has been developed. In this reaction, 3,3-difluoroallyl alcohol was used as a fluorine-containing building block to construct the C–CF2 bond for the first time. This approach is recognized for its robust tolerance of functional groups, impressive yields, and excellent atomic efficiency, all achieved under mild reaction conditions. A series of β,β-difluoromethyleneamide derivatives were efficiently obtained through simple operations, and their practicality was confirmed through gram-scale synthesis and product derivatization.