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Fe (6-Me-PyTACN)-catalyzed, one-pot oxidative cleavage of methyl oleate and oleic acid into carboxylic acids with H2O2 and NaIO 4

The first Fe-based catalytic system for the oxidative cleavage of unsaturated fatty acids and esters to carboxylic acids is reported. The system comprises [Fe(OTf)(2)(6-Me-PyTACN)] (2) (6-Me-PyTACN = 1-[(6-methyl-2-pyridyl) methyl]-4,7-dimethyl-1,4,7-triazacyclononane, OTf = trifluoromethane sulfonate anion) as the catalyst (3 mol%) either with a combination of hydrogen peroxide and NaIO4 or exclusively with NaIO4 as the oxidant, and operates at 0 degrees C or ambient temperature. Under these standard conditions (method A), methyl oleate is converted in a one-pot procedure into 50-55% of both nonanoic and azelaic acid, together with some epoxide and aldehyde intermediates as byproducts. These yields can be further improved by addition of sulfuric acid (method B) to hydrolyze the epoxide byproducts, by including a pH neutralization step and addition of more catalyst (1 mol%). Under the optimized conditions, both methyl oleate and oleic acid are converted into high yields of the corresponding carboxylic acids (80-85%). Overall, this catalytic system provides an alternative to the industrial ozonolysis of oleic acid and to catalytic Ru-and Os-based systems for the oxidative cleavage of unsaturated fatty acids and ester

B.M.W. and R.J.M.K.G. acknowledge Utrecht University for financial support through its ’Focus and Massa’ program. M.C. acknowledges financial support from the European Research Council (ERC-2009-StG-239910), MINECO of Spain (CTQ2012-37420-C02-01/BQU, Consolider-Ingenio CSD2010-00065) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637 and ICREA Academia Award). The X-ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO)

info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/

Royal Society of Chemistry (RSC)

Manager: European Research Council
Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Ministerio de Ciencia e Innovación (Espanya)
Author: Spannring, Peter
Prat Casellas, Irene
Costas Salgueiro, Miquel
Lutz, Martin
Bruijnincx, Pieter C A
Weckhuysen, Bert M.
Klein Gebbink, Robertus J M
Abstract: The first Fe-based catalytic system for the oxidative cleavage of unsaturated fatty acids and esters to carboxylic acids is reported. The system comprises [Fe(OTf)(2)(6-Me-PyTACN)] (2) (6-Me-PyTACN = 1-[(6-methyl-2-pyridyl) methyl]-4,7-dimethyl-1,4,7-triazacyclononane, OTf = trifluoromethane sulfonate anion) as the catalyst (3 mol%) either with a combination of hydrogen peroxide and NaIO4 or exclusively with NaIO4 as the oxidant, and operates at 0 degrees C or ambient temperature. Under these standard conditions (method A), methyl oleate is converted in a one-pot procedure into 50-55% of both nonanoic and azelaic acid, together with some epoxide and aldehyde intermediates as byproducts. These yields can be further improved by addition of sulfuric acid (method B) to hydrolyze the epoxide byproducts, by including a pH neutralization step and addition of more catalyst (1 mol%). Under the optimized conditions, both methyl oleate and oleic acid are converted into high yields of the corresponding carboxylic acids (80-85%). Overall, this catalytic system provides an alternative to the industrial ozonolysis of oleic acid and to catalytic Ru-and Os-based systems for the oxidative cleavage of unsaturated fatty acids and ester
B.M.W. and R.J.M.K.G. acknowledge Utrecht University for financial support through its ’Focus and Massa’ program. M.C. acknowledges financial support from the European Research Council (ERC-2009-StG-239910), MINECO of Spain (CTQ2012-37420-C02-01/BQU, Consolider-Ingenio CSD2010-00065) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637 and ICREA Academia Award). The X-ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO)
Format: application/pdf
Document access: http://hdl.handle.net/10256/10914
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1039/c3cy00851g
info:eu-repo/semantics/altIdentifier/issn/2044-4753
info:eu-repo/semantics/altIdentifier/eissn/2044-4761
MICINN/PN 2010-2016/CSD2010-00065
AGAUR/2009-2014/2009 SGR-637
info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
Is part of: info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/
Rights: Tots els drets reservats
Subject: Catàlisi
Catalysis
Catalitzadors
Catalysts
Oxidació
Oxidation
Title: Fe (6-Me-PyTACN)-catalyzed, one-pot oxidative cleavage of methyl oleate and oleic acid into carboxylic acids with H2O2 and NaIO 4
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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