Abstract The anomeric effect associated with the nitrogen atom in the isocyano group was investigated by using 1 H NMR spectroscopic analysis of an anomeric pair of xylopyranosyl isocyanides 8 and 7. We found that β-anomer 7 prefers to exist in the 1 C 4 conformation in which the nitrogen atom in the isocyano group adopts an axial orientation. This observation, coupled with the results of X-ray crystallographic analysis establishes that the nitrogen ...