The first direct catalytic asymmetric synthesis of gamma-amino ketones was realized by the development of a highly diastereoselective and enantioselective C-C bond-forming umpolung reaction of imines and enones under the catalysis of a new cinchona alkaloid-derived phase-transfer catalyst. In a loading ranging from 0.02 to 2.5 mol %, the catalyst activates a broad range of trifluoromethyl imines and aldimines as nucleophiles to engage in chemo-, regio-, diastereo- and enantioselective C-C bond-forming reactions with acyclic and cyclic enones, thereby converting these readily available prochiral starting materials into highly enantiomerically enriched chiral gamma-amino ketones in synthetically useful yields. Enabled by this unprecedented umpolung reaction of imines, conceptually new and concise routes were developed for the asymmetric synthesis of nitrogen heterocycles such as pyrrolidines and indolizidines.