HIGHLY SELECTIVE NITROXYL RADICAL-MEDIATED OXIDATION OF PRIMARY ALCOHOL GROUPS IN WATER-SOLUBLE GLUCANS

被引：475

作者：

DENOOY, AEJ

BESEMER, AC

VANBEKKUM, H

机构：

[1] TNO,NUTR & FOOD RES INST,DEPT BIOCHEM,3700 AJ ZEIST,NETHERLANDS

[2] DELFT UNIV TECHNOL,ORGAN CHEM & CATALYSIS LAB,2628 BL DELFT,NETHERLANDS

来源：

CARBOHYDRATE RESEARCH | 1995年 / 269卷 / 01期

关键词：

OXIDATION; PRIMARY ALCOHOL; URONIC ACID PREPARATION; TEMPO OXIDATION BY; PULLULAN;

D O I：

10.1016/0008-6215(94)00343-E

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

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 H-1 and C-13 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.

引用

页码：89 / 98

页数：10