Cu/Pd Synergistic Dual Catalysis: Asymmetric α-Allylation of an α-CF₃ Amide

Despite the burgeoning demand for fluorine-containing chemical entities, the construction of CF₃ -containing stereogenic centers has remained elusive. Herein, we report the strategic merger of Cu^I /base-catalyzed enolization of an α-CF₃ amide and Pd⁰ -catalyzed allylic alkylation in an enantioselective manner to deliver chiral building blocks bearing a stereogenic carbon center connected to a CF₃ , an amide carbonyl, and a manipulable allylic group. The phosphine complexes of Cu^I and Pd⁰ engage in distinct catalytic roles without ligand scrambling to render the dual catalysis operative to achieve asymmetric α-allylation of the amide. The stereoselective cyclization of the obtained α-CF₃ -γ,δ-unsaturated amides to give tetrahydropyran and γ-lactone-fused cyclopropane skeletons highlights the synthetic utility of the present catalytic method as a new entry to non-racemic CF₃ -containing compounds.