C-Glycosylmethylene carbenes: synthesis of anhydro-aldose tosylhydrazones as precursors; generation and a new synthetic route to exo-glycals

Abstract

Acylated anhydro-aldononitriles (glycosyl cyanides) were transformed into anhydro-aldose tosylhydrazones by Raney–nickel reduction in the presence of tosylhydrazine in a one-pot reaction. The configuration of the CN double bond in these hydrazones was E as proven by ¹⁵N–¹H coupling constants as well as X-ray crystallography. Thermolysis in refluxing 1,4-dioxane of the sodium salts of the tosylhydrazones obtained by sodium hydride (generally 10 eq.) resulted in the formation of anhydro-1-deoxy-ald-1-enitols (exo-glycals). “Dimeric” N-glycosylmethyl anhydro-aldose tosylhydrazones could also be isolated when the use of less base caused incomplete deprotonation of the starting compounds. This two-step procedure constitutes a novel, reasonably short synthetic pathway to acylated exo-glycals from the readily available glycosyl cyanides.