352310-78-2

Upstream product

• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 52443-07-9 3,4,5,7-tetra-O-acetyl-2,6-anhydro-D-glycero-L-manno-heptonitrile 

Downstream Products

• 62771-95-3 3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D-galacto-hept-1-enitol 
• 30906-26-4 3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D-glycero-L-manno-heptitol 

Relevant academic research and scientific papers

exo-Glycals from glycosyl cyanides. First generation of C-glycosylmethylene carbenes from 2,5- and 2,6-anhydroaldose tosylhydrazones

In a one-pot reaction acylated glycosyl cyanides were transformed with Raney nickel-sodium hypophosphite into 2,5- and 2,6-anhydroaldose tosylhydrazones, which gave exo-glycals under Bamford-Stevens conditions.

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

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 C=N 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-glycosyl-methyl 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.