Two chiral diarylmethylamines with a phenolic hydroxy group at their ortho positions (1c and Id) were synthesized, and their direct enantioseparation via diastereomeric salt formation was investigated. Crystallographic analyses of the diastereomeric salts involving 1c were conducted: water molecules incorporated in the space played an important role in chiral recognition. Enantiopure 1 were applied for the enantioselective addition of diethylzinc to benzaldehyde. Ligand (R)-1d afforded the product in very high yield (96%) and enantiopurity (92% ee). Not only the phenyl group on the stereogenic center of (R) 1d but also its bulky tert-butyl group is important for chiral induction. (C) 2016 Elsevier Ltd. All rights reserved.