SELECTIVE OXIDATION OF PRIMARY ALCOHOLS MEDIATED BY NITROXYL RADICAL IN AQUEOUS-SOLUTION - KINETICS AND MECHANISM

被引：203

作者：

DENOOY, AEJ ^{[1
]}

BESEMER, AC ^{[1
]}

VANBEKKUM, H ^{[1
]}

机构：

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

来源：

TETRAHEDRON | 1995年 / 51卷 / 29期

关键词：

D O I：

10.1016/0040-4020(95)00417-7

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The kinetics of the TEMPO-mediated oxidation of methyl alpha-D-glucopyranoside to sodium methyl alpha-D-glucopyranosiduronate were studied. An intermediate was found which was identified as the hydrated aldehyde. This was oxidised in the same manner as the alcohol, with pseudo first order rate constants ratio k(obs,ald)/k(obs,alc) approximate to 7. The reaction mechanism is discussed with emphasis on steric factors and compared to literature data. Two different reaction pathways are postulated; under basic reaction conditions via a cyclic transition state 3 and under acid reaction conditions through an acyclic transition state 4.

引用

页码：8023 / 8032

页数：10

共 20 条

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