Comparison of TEMPO and its derivatives as mediators in laccase catalysed oxidation of alcohols

被引：119

作者：

Arends, Isabel W. C. E. ^{[1
]}

Li, Yu-Xin ^{[1
]}

Ausan, Rina ^{[1
]}

Sheldon, Roger A. ^{[1
]}

机构：

[1] Delft Univ Technol, Lab Biocatalysis & Organ Chem, Dept Biotechnol, NL-2628 BL Delft, Netherlands

来源：

TETRAHEDRON | 2006年 / 62卷 / 28期

关键词：

laccase; TEMPO; alcohol oxidation; nitroxyl radical;

D O I：

10.1016/j.tet.2005.12.076

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of TEMPO (2,2',6,6'-tetramethylpiperidinyl-1-oxy) derivatives were studied as mediators of laccase (from Trametes versicolor) in the oxidation of benzyl alcohol and 1-phenylethyl alcohol. TEMPO (1), 4-hydroxy-TEMPO (2) and 4-acetylamino-TEMPO (4) turned out to be the most active mediators for laccase. In addition. 4-acetylamino-TEMPO and 4-hydroxy-TEMPO were more active in the oxidation of 1-phenylethanol compared to TEMPO. For these mediators kinetic isotope effects in the range of 2.1-3.2 were observed for alpha-monodeutero-p-methylbenzyl alcohol oxidation. These values are consistent with a mechanism involving oxoammonium intermediacy. Competition experiments between benzyl alcohol and I-phenylethanol showed that TEMPO and its derivatives react faster with primary alcohols than with secondary alcohols, also in line with the proposed mechanism. (c) 2006 Elsevier Ltd. All rights reserved.

引用

页码：6659 / 6665

页数：7

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