Solkane (R) 365mfc (1,1,1,3,3-pentafluorobutane, CF3CH2CF2CH3) is proven to be an environmental benign alternative solvent for the catalytic enantioselective trifluoromethylation of azomethine imines 1. High chemical yields and enantioselectivities (up to 96% ee) were achieved by employing previously unknown and structurally simple cinchona alkaloid ammonium salt, N-2-iodobenzylcinchoninium bromide 3d as a catalyst. (C) 2012 Elsevier B.V. All rights reserved.