Despite the burgeoning demand for fluorine-containing chemical entities,t he construction of CF 3 -containing stereogenic centers has remained elusive.Herein, we report the strategic merger of Cu I /base-catalyzed enolization of an a-CF 3 amide and Pd 0 -catalyzed allylic alkylation in an enantioselective manner to deliver chiral building blocks bearing astereogenic carbon center connected to aC F 3 ,a na mide carbonyl, and amanipulable allylic group.The phosphine complexes of Cu I and Pd 0 engage in distinct catalytic roles without ligand scrambling to render the dual catalysis operative to achieve asymmetric a-allylation of the amide.T he stereoselective cyclization of the obtained a-CF 3 -g,d-unsaturated amides to give tetrahydropyran and g-lactone-fused cyclopropane skeletons highlights the synthetic utility of the present catalytic method as an ew entry to non-racemic CF 3 -containing compounds.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme 3. Transformation of the a-allylated product 3a.a )NIS, TFA, CH 2 Cl 2 /H 2 O, RT,24h.b)DBU, toluene, RT,7 7% (2 steps). c) BH 3 ·NH 3 ,L DA, THF, 0 8 8Ct oRT, 1h,8 0%.d )Ph 3 P=S(10 mol %), NBS, AcOH, CH 2 Cl 2 , À20 8 8C, 91 %(87/13 d.r.). NIS = N-iodosuccinimide, TFA = trifluoroacetic acid, LDA = lithium diisopropylamide, NBS = N-bromosuccinimide.