Twelve N-glycosyl amines were synthesised using 4,6-O-benzylidene-D-glucopyranose and different substituted aromatic amines, including some diamines that resulted in bis-glycosyl amines. Another set of six N-glycosyl amines was synthesised using different hexoses and pentoses and 2-(o-aminophenyl)benzimidazole. All compounds were isolated as solid products and purified, their elemental compositions were established, and these were characterised by NMR (1H and 13C), UV-Vis, and FTIR spectroscopy, by FAB mass spectrometry (molecular-ion peaks gave molecular weights), and by their optical rotations. While the protected saccharide, 4,6-O-benzylidene-D-glucopyranose, exists as a mixture of β and α anomers in solution, the corresponding N-glycosyl amines were of only the β anomeric form as determined by NMR and FTIR spectroscopy. On the other hand, N-glycosyl amines synthesised from 2-(o-aminophenyl)benzimidazole prefer the α anomeric form, and in two cases a mixture of both the β and the α anomers were observed. The trends observed in the chemical shifts were compared among different products. © 2001 Elsevier Science Ltd. All rights reserved.