Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide

Abstract

A new procedure is described for the synthesis of α,β-glycosyl cyanides by the reaction of per-O-benzylated S-α-ᴅ-glycopyranosyl phosphorothioates with trimethylsilyl cyanide in the presence of Lewis acid. Starting S-glycosyl phosphorothioates are prepared, directly, from O-benzyl protected reducing D-hexopyranoses (gluco-, galacto-, manno-) and alkylammonium salt of phosphorothioic acid under Lewis acid catalysis.

Improved preparation of 4(5)-aryl-2-(β-d-glucopyranosyl)-imidazoles, the most efficient glucose analogue inhibitors of glycogen phosphorylase

“…O-Perbenzylated D-glucopyranosyl cyanides both in aand b-congurations are known from the literature. [16][17][18][19] While the…”

The synthesis of d-C-mannopyranosides

“…With a sulfide or phosphate in the anomeric position, Lewis acidic activation generating an oxonium moiety is required for introduction of the cyano group (Table 6) [102][103][104].…”