Glycosylation of organic phosphorus thio- and selenoacids—II: The reaction of organic phosphorus thioselenoacids with glycosyl bromides under kinetically and thermodynamically controlled conditions

Abstract

Ambident anions derived from phosphorus thioselcnoacids were glycosylated with 2,3,4,6 - tetra - O - acetyl - α - d - glucopyranosyl bromide, 2,3,4,6 - tetra - O - acetyl - α - d - galactopyranosyl bromide and 2,3,4 - tri- O - acetyl - α - d - xylopyranosyl bromide. The products were β-Se-glucosyl- and β-S-glucosylthioselenoates. The Se/S ratio of the glycosylated phosphorothioselenoates depends on the reaction conditions. At higher temperatures an equilibrium was observed. As a result of this equilibrium the Se/S ratio of the linkages formed in the glycosylated products was different from that observed under kinetic control. The structures of the glycosylated phosphorothioselenoates were confirmed by spectroscopy, independent synthesis and selective oxidation.