Enantioselective Di-/Perfluoroalkylation of β-Ketoesters Enabled by Cooperative Photoredox/Nickel Catalysis

Efficient and enantioselective radical difluoroalkylation and perfluoroalkylation reactions of β-ketoesters were successfully developed through an asymmetric photoredox and nickel catalysis cascade. This protocol provides R_f-containing quaternary stereocenters in up to 67% yield and 95:5 er with ethyl iododifluoroacetate and perfluoroalkyl iodides (C₃F₇I and C₄F₉I) as radical sources under extremely mild conditions.