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

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

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

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)

Wiley

Manager: Ministerio de Economía y Competitividad (Espanya)
Ministerio de Ciencia e Innovación (Espanya)
Author: Serrano Plana, Joan
Aguinaco, Almudena
Belda, Raquel
García-España, Enrique
Basallote, Manuel G.
Company Casadevall, Anna
Costas Salgueiro, Miquel
Abstract: 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
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
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)
Document access: http://hdl.handle.net/2072/298592
Language: eng
Publisher: Wiley
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: Recercat

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