Synthesis of N-glycosyl amides: conformational analysis and evaluation as inhibitors of ß-galactosidase from E. coli.

The synthesis of N-glycosyl amides typically involves the use of glycosyl amines as direct precursors, resulting in low yields due to hydrolysis and the loss of stereocontrol through anomerization processes. In this study, a sequential synthesis of N-glycosyl amides is proposed, employing glycosyl amines as intermediates obtained from glycosyl azides. Derivatives with gluco, galacto, or xylo configurations were synthesized. Hexose derivatives were obtained under stereocontrol to give only the ß anomer, while the xylo derivatives provided a mixture of α and ß anomers. Conformational analysis revealed that all ß anomers adopted the 4C1 conformation, while α anomers were found in the 1C4 chair as the major conformer. After de-O-acetylation, the derivatives containing a galactose unit were evaluated as inhibitors of ß-galactosidase from E. coli and were found to be moderate inhibitors.

Photooxidation of thiosaccharides mediated by sensitizers in aerobic and environmentally friendly conditions.

A series of ß-d-glucopyranosyl derivates have been synthesized and evaluated in photooxidation reactions promoted by visible light and mediated by organic dyes under aerobic conditions. Among the different photocatalysts employed, tetra-O-acetyl riboflavin afforded chemoselectively the respective sulfoxides, without over-oxidation to sulfones, in good to excellent yields and short reaction times. This new methodology for the preparation of synthetically useful glycosyl sulfoxides constitutes a catalytic, efficient, economical, and environmentally friendly oxidation process not reported so far for carbohydrates.