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Exceedingly fast oxygen atom transfer to olefins via a catalytically competent nonheme iron species

The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at −40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(O)(OAc)(PyNMe3)]2+, in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the substrate on the reaction rate could be elucidated, and the relative reactivities determined for the catalytic oxidations could be reproduced by kinetic studies. The observed fast reaction rates and high selectivities demonstrate that this metastable compound is a truly competent OAT intermediate of relevance for nonheme iron catalyzed epoxidations

El mateix article està publicat en alemany a l’edició alemanya d’ ’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 21, p.6418–6422. DOI http://dx.doi.org/10.1002/ange.201601396

Financial support for this work was provided by the EuropeanCommission (2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), the Spanish Ministry of Science (CTQ2012-37420-C02-01/BQU to M.C., CTQ2012-37821-C02-02 to M.G.B., CTQ2013-43012-P to A.C., CTQ2013-48917-C3-1-P to R.B. and E.G.-E.), the Unidad de Excelencia (MDM 2015-0038 and CSD2010-00065 to M.C., M.G.B., R.B., and E.G.-E), the Generalitat Valenciana (PROMETEOII 2015/002t to R.B. and E.G.-E.), and the Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014SGR-862). The Spanish Ministry of Science is also acknowledged for a Ramýn y Cajal contract to A.C. (RYC-2011-08683)

© Angewandte Chemie - International Edition, 2016, vol. 55, núm. 22,p. 6310-6314

Wiley

Author: Serrano Plana, Joan
Aguinaco, Almudena
Belda, Raquel
García-España, Enrique
Basallote, Manuel G.
Company Casadevall, Anna
Costas Salgueiro, Miquel
Date: 2016 May 17
Abstract: The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at −40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(O)(OAc)(PyNMe3)]2+, in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the substrate on the reaction rate could be elucidated, and the relative reactivities determined for the catalytic oxidations could be reproduced by kinetic studies. The observed fast reaction rates and high selectivities demonstrate that this metastable compound is a truly competent OAT intermediate of relevance for nonheme iron catalyzed epoxidations
El mateix article està publicat en alemany a l’edició alemanya d’ ’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 21, p.6418–6422. DOI http://dx.doi.org/10.1002/ange.201601396
Financial support for this work was provided by the EuropeanCommission (2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), the Spanish Ministry of Science (CTQ2012-37420-C02-01/BQU to M.C., CTQ2012-37821-C02-02 to M.G.B., CTQ2013-43012-P to A.C., CTQ2013-48917-C3-1-P to R.B. and E.G.-E.), the Unidad de Excelencia (MDM 2015-0038 and CSD2010-00065 to M.C., M.G.B., R.B., and E.G.-E), the Generalitat Valenciana (PROMETEOII 2015/002t to R.B. and E.G.-E.), and the Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014SGR-862). The Spanish Ministry of Science is also acknowledged for a Ramýn y Cajal contract to A.C. (RYC-2011-08683)
Format: application/pdf
ISSN: 1433-7851 (versió paper)
1521-3773 (versió electrònica)
Document access: http://hdl.handle.net/10256/13198
Language: eng
Publisher: Wiley
Collection: MINECO/PN 2013-2015/CTQ2012-37420-C02-01
MICINN/PN 2010-2016/CSD2010-00065
MINECO/PE 2014-2016/CTQ2013-43012-P
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/anie.201601396
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/303522
info:eu-repo/grantAgreement/EC/FP7/239910
Is part of: © Angewandte Chemie - International Edition, 2016, vol. 55, núm. 22,p. 6310-6314
Rights: Tots els drets reservats
Subject: Epòxids
Epoxy compounds
Alquens
Alkenes
Ferro
Iron
Title: Exceedingly fast oxygen atom transfer to olefins via a catalytically competent nonheme iron species
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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