Mild homogeneous oxidation of alkanes and alcohols including glycerol with tert-butyl hydroperoxide catalyzed by a tetracopper(II) complex

Author(s)

Kirillova, Marina V. ^[1] ; Kirillov, Alexander M. ^[1] ; Mandelli, Dalmo ^{[2, 3]} ; Carvalho, Wagner A. ^[2] ; Pombeiro, Armando J. L. ^[1] ; Shul'pin, Georgiy B. ^[4]

Affiliation

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

^[2] Univ Fed ABC, Ctr Ciencias Nat & Humanas, BR-09090400 Santo Andre, SP - Brazil

^[3] Pontificia Univ Catolica Campinas, Fac Quim, BR-13086900 Campinas, SP - Brazil

^[4] Russian Acad Sci, NN Semenov Chem Phys Inst, Moscow 119991 - Russia

• Document type: Journal article
• Source: JOURNAL OF CATALYSIS; v. 272, n. 1, p. 9-17, MAY 25 2010.
• Web of Science Citations: 65

Abstract

The homogeneous catalytic system composed of the aqua-soluble tetracopper(II) triethanolaminate complex {[}O subset of Cu(4)[N(CH(2)CH(2)O)(3)](4)(BOH)(4)]{[}BF(4)](2) (1), t-BuOOH (TBHP), water and acetonitrile solvent (optional) has been applied for the mild oxidation of (i) linear and cyclic alkanes to the corresponding alkyl peroxides, alcohols and ketones, (ii) secondary or primary alcohols to ketones or aldehydes, respectively and (iii) glycerol (GLY) to dihydroxyacetone (DHA). Unusual regio-, bond and stereoselectivity parameters have been determined for the alkane oxygenations and discussed in terms of possible steric, hydrophobic and electronic effects. In alcohol oxidations, secondary alcohols are the most reactive substrates. Yields and TONs up to 82% and 1200, respectively, have been obtained in the oxidation of isopropanol to acetone. The selective oxidation of GLY to DHA by the 1/TBHP system has been also achieved, although providing lower conversions. The 1/H(2)O(2) system for the GLY oxidation is particularly advantageous in terms of selectivity and oxidant efficiency. These systems constitute one of the first examples of a metal-catalyzed oxidation of glycerol under homogeneous conditions. (C) 2010 Elsevier Inc. All rights reserved. (AU)

• FAPESP's process: 06/03996-6 - Oxidation of organic compounds including natural products catalysed by transitions metals: Mn, Os and Cu
• Grantee: Dalmo Mandelli
• Support Opportunities: Regular Research Grants