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 Rf-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.