The cationic complex [Pd(pi-Allyl)(Isosparteine)](+) PF6- was found to be a suitable catalyst for asymmetric alkylation of allylic acetates. Asymmetric allylic alkylation with NaCH(CO(2)Me)(2) was carried out in the presence of a 5 mol % of the catalyst to give chiral alkylation products with high enantiomeric excesses.