Mild aerobic oxidation of benzyl alcohols to benzaldehydes in water catalyzed by aqua-soluble multicopper(II) triethanolaminate compounds

被引：80

作者：

Figiel, Pawel J. ^{[1
]}

Kirillov, Alexander M. ^{[1
]}

Karabach, Yauhen Yu. ^{[1
]}

Kopylovich, Maximilian N. ^{[1
]}

Pombeiro, Armando J. L. ^{[1
]}

机构：

[1] Univ Tecn Lisboa, Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon, Portugal

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2009年 / 305卷 / 1-2期

关键词：

Dioxygen; TEMPO; Copper(II) complexes; Aqueous medium; Homogeneous catalysis; PEROXIDATIVE OXIDATION; COORDINATION POLYMER; ALDEHYDES; KETONES; GREEN; CU; CYCLOALKANES; TRINUCLEAR; COMPLEXES; DINUCLEAR;

D O I：

10.1016/j.molcata.2009.01.002

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The aqua-soluble multinuclear copper(II) compounds [Cu-2(mu-H(2)tea)(2){mu(3)-Na-2(H2O)(4)}(mu(6)-pma)](n)center dot 10nH(2)O (1) and [O subset of Cu-4(tea)(4)(BOH)(4)][BF4](2) (2) (H-3 tea = triethanolamine, H(4)pma = pyromellitic acid) have been applied as efficient catalysts for the mild, selective and clean oxidation of benzyl alcohols to benzaldehydes, which proceeds in sole water as solvent at 50 degrees C, under atmospheric pressure of air(or O-2) as oxidant, and is mediated by TEMPO radical. Molar yields of benzaldehydes (based on alcohol) up to 99% have been achieved (with a high selectivity). Attractive features of these catalytic systems include the use of organic-solvent-free reaction medium, air or dioxygen as oxidant, and aqua-soluble copper catalysts that are readily available by self-assembly. (C) 2009 Elsevier B.V. All rights reserved.

引用

页码：178 / 182

页数：5

共 32 条

[1]

[Anonymous], 2002, Ullmann's Encyclopedia of Industrial Chemistry

[2] TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6] [J].

Ansari, IA ;

Gree, R .

ORGANIC LETTERS, 2002, 4 (09) :1507-1509

[3]

Arends I.W. C. E., 2004, Modern Oxidation Methods, P83

[4] Efficient Mn-Cu and Mn-Co-TEMPO-catalysed oxidation of alcohols into aldehydes and ketones by oxygen under mild conditions [J].

Cecchetto, A ;

Fontana, F ;

Minisci, F ;

Recupero, F .

TETRAHEDRON LETTERS, 2001, 42 (38) :6651-6653

[5] Redox potentiometry studies of particulate methane monooxygenase: Support for a trinuclear copper cluster active site [J].

Chan, Sunney I. ;

Wang, Vincent C-C ;

Lai, Jeff C. -H. ;

Yu, Steve S. -F ;

Chen, Peter P. -Y ;

Chen, Kelvin H. -C ;

Chen, Chang-Li ;

Chan, Michael K. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (12) :1992-1994

[6] Cu(II)-nitroxyl radicals as catalytic galactose oxidase mimics [J].

Dijksman, A ;

Arends, IWCE ;

Sheldon, RA .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (18) :3232-3237

[7] TEMPO-copper(II) diimine-catalysed oxidation of benzylic alcohols in aqueous media [J].

Figiel, Pawel J. ;

Leskela, Markku ;

Repo, Timo .

ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (07) :1173-1179

[8] Room temperature aerobic copper-catalysed selective oxidation of primary alcohols to aldehydes [J].

Gamez, P ;

Arends, IWCE ;

Sheldon, RA ;

Reedijk, J .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (07) :805-811

[9] Copper(II)-catalysed aerobic oxidation of primary alcohols to aldehydes [J].

Gamez, P ;

Arends, IWCE ;

Reedijk, J ;

Sheldon, RA .

CHEMICAL COMMUNICATIONS, 2003, (19) :2414-2415

[10] Multicopper(II) Pyromellitate Compounds: Self-Assembly Synthesis, Structural Topologies, and Magnetic Features [J].

Karabach, Yauhen Y. ;

Kirillov, Alexander M. ;

Haukka, Matti ;

Sanchiz, Joaquin ;

Kopylovich, Maximilian N. ;

Pombeiro, Armando J. L. .

CRYSTAL GROWTH & DESIGN, 2008, 8 (11) :4100-4108

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