Influence of the oxime and anomeric configurations on the stability of 2-deoxy-2-hydroxyimino-D-hexopyranosides

Article abstract of DOI:10.1016/j.molstruc.2016.07.019

The Z/E isomerisations of the synthesized benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-hydroxyimino-D-hexopyranosides during the NMR measurement and during the Zemplén O-deacetylation were observed. In order to study stabilities and tendency of the obtained compounds to isomerise, B3LYP/6-311++G^?? level geometry optimisations for four stereoisomers of methyl 2-deoxy-2-hydroxyimino-D-arabino-hexopyranosides in both the O-acetylated and O-deacetylated forms were performed. The results of our theoretical studies are fully in agreement with the experimental data and NMR analysis. Additionally, a single-crystal X-ray diffraction data for benzyl 2-deoxy-2-hydroxyimino-α-D-lyxo-hexopyranoside are reported to supplement our theoretical studies.