Chiral Cu(II) complexes were generated in situ by the interaction of aminoalcohol based ligands L-1-L-6 derived from (1R,2S)-(-)-2-aminodiphenylethanol, (1R,25)-1-amino-2,3-dihydro-1H-inden-2-ol, (R or S)-valinol and (S)-2-amino-1,1-diphenylpropan-1-ol with 4-tert-butyl-2,6-diformylphenol and screened for aza-Henry reaction of a variety of aromatic, aliphatic N-tosylaldimine and aromatic N-benzenesulfonamide aldimine in toluene at RT. Excellent enantioselectivity, diastereoselectivity (99%) of beta-nitro-N-tosylaldamine with good yield (80%) was achieved in case of complex L-2-Cu(II) with low catalyst loading. The enantio-pure aza-Henry product obtained was straightforwardly transformed into the enantioenriched chiral vicinal diamine (ee; 96%) with good yield in successive two steps and was further used for the synthesis of (S)-levamisole (an anthelminthic agent). The catalytic system worked well up to five cycles with retention of enantioselectivity. (C) 2015 Elsevier B.V. All rights reserved.