An atom-economic and highly efficient vinylogous umpolung strategy is developed for deconjugated carbonyl compounds,w hich generate electron-deficient p-allylpalladium complexes with Pd(OAc) 2 under ligand-free conditions. In cooperation with ac hiral-phosphonium-based phase-transfer catalyst, the asymmetric direct oxidative allylic alkylations of 3-substituted oxindoles are furnished under O 2 atmosphere. The g-oreven remote e-regioselective alkylation products,with substantial substituents,are delivered with excellent enantioselectivity,a nd can be further used to access diverse chiral spirocyclic architectures effectively.T he Mukaiyama dienol silyl ether can be utilized similarly,i ndicating that the current active p-allylpalladium species results from tautomerization of the Pd II -dienolate intermediate. Scheme 1. Diverse activationm odes for unsaturated systems. EWG = electron-withdrawing group.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.