The β-isocupreidine, a cinchonine derived alkaloid, catalyzed asymmetric S_N2′–S_N2′ reaction between N-2,2,2-trifluoroethylisatin ketimines and MBH type carbonates was realized in a simple and efficient way. A series of chiral α-trifluoromethylamines were prepared with excellent yields and stereoselectivities. A subsequent and easy process of deprotection gave γ-trifluoromethyl-α-methylenelactam in a stereoselective manner.