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 CuI/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 CuI 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. A strategic merger of CuI/base‐catalyzed enolization of an α‐CF3 amide and Pd0‐catalyzed allylic alkylation to give enantioselective α‐allylation of the amide was developed. This method delivers chiral building blocks bearing a stereogenic carbon center connected to a CF3, an amide carbonyl, and an allylic group. Phosphine complexes of CuI and Pd0 engaged in distinct catalytic roles without ligand scrambling to produce cooperative dual catalysis.