Asymmetric allylic alkylations have been well explored; however, the enantioselective construction of all-carbon quaternary centers still remains a challenging goal. Using γ-acetoxy-α,β-unsaturated carbonyl compounds as π-allyl precursor and cyclic β-ketoesters as nucleophile in the presence of a Pd catalyst, Zn additive and chiral diaminophosphine oxide ligand (DIAPHOX), a variety of quaternary carbon compounds were synthesized with good to excellent enantioselectivity.