Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans

With catalytic amounts of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and hypochlorite/bromide as the regenerating oxidant in water, primary alcohol groups in glucans and derivatives thereof were rapidly and completely oxidised. For pyranosides, selectivity was higher than 95% and no side products...

Full description

Saved in:
Bibliographic Details
Published in:Carbohydrate research 1995-04, Vol.269 (1), p.89-98
Main Authors: de Nooy, Arjan E.J., Besemer, Arie C., van Bekkum, Herman
Format: Article
Language:English
Subjects:
bromides
glucose
organic nitroxyl radicals
oxidants
Oxidation
polysaccharides
potato starch
Primary alcohol
Pullulan
TEMPO oxidation by
trehalose
Uronic acid preparation
uronic acids
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:With catalytic amounts of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and hypochlorite/bromide as the regenerating oxidant in water, primary alcohol groups in glucans and derivatives thereof were rapidly and completely oxidised. For pyranosides, selectivity was higher than 95% and no side products could be detected with 1H and 13C NMR or with high-performance anion-exchange chromatography (HPAEC). The optimum pH for the reaction was between 10 and 11. The oxidation was found to be first order in TEMPO and Br −. The oxidation method can be applied to determine the amount of primary alcohol groups in water-soluble glucans; for pullulan, a proportion of 70% and for dextran, a proportion of 3% primary alcohol groups was found.
ISSN:0008-6215
1873-426X
DOI:10.1016/0008-6215(94)00343-E