A novel enantioselective synthetic method for the construction of a quaternary carbon center from malonates via phase-transfer catalytic (PTC) alkylation has been developed. The asymmetric alpha-alkylation of diphenylmethyl tertbutyl alpha-alkylmalonates with alkylating agents under phase-transfer catalysis conditions (aq 50% KOH, toluene, 0 degrees C) in the presence of (S,S)-3,4,5-trifluorophenyl-NAS bromide (8) as PTC catalyst afforded the corresponding alpha,alpha-dialkylmalonates in high chemical (up to 99%) and optical yields (up to 97% ee) which could be readily converted to versatile chiral intermediates. Notably, the direct double alpha-alkylations of diphenylmethyl tert-butyl malonate also provided the corresponding alpha,alpha-dialkylmalonates without loss of enantioselectivity. The synthetic potential of this method has been demonstrated by the preparation of alpha,alpha-dialkylamino acid and oxindole systems.