The first example of asymmetric hydrogenation of imines using Co-2(CO)(8)/(R)-BINAP/H-2/CO system was developed. The reaction conditions were screened with a wide range of N-aryl benzophenone ketimines, obtaining products with excellent yields and good enantiomeric excess. Moreover, a pathway is suggested based on the isolation and characterization of several catalyst intermediates. (c) 2012 Elsevier B.V. All rights reserved.