A palladium-catalyzed asymmetric decarboxylative reaction of racemic gamma-methylidene-delta-valerolactones with aryl isocyanates has been developed to give enantioenriched 3,3-disubstituted 2-piperidones. High enantioselectivity has been achieved by tuning the ester group on Substrate and the substituents of phosphoramidite ligand.