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...

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Bibliographic Details
Published inCarbohydrate research Vol. 269; no. 1; pp. 89 - 98
Main Authors de Nooy, Arjan E.J., Besemer, Arie C., van Bekkum, Herman
Format Journal Article
LanguageEnglish
Published Elsevier Ltd 03.04.1995
Subjects
bromides
glucose
organic nitroxyl radicals
oxidants
Oxidation
polysaccharides
potato starch
Primary alcohol
Pullulan
TEMPO oxidation by
trehalose
Uronic acid preparation
uronic acids
Uronic acid preparation
Pullulan
Oxidation
TEMPO oxidation by
Primary alcohol
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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