2026-04-14T02:10:13Zhttps://recercat.cat/oai/requestoai:recercat.cat:10256/131982024-06-18T13:52:06Zcom_2072_452955com_2072_2054col_2072_453073
RECERCAT
author
Serrano Plana, Joan
author
Aguinaco, Almudena
author
Belda, Raquel
author
García-España, Enrique
author
Basallote, Manuel G.
author
Company Casadevall, Anna
author
Costas Salgueiro, Miquel
2024-06-18T13:52:06Z
2024-06-18T13:52:06Z
info:eu-repo/date/embargoEnd/2026-01-01info:eu-repo/date/embargoEnd/2026-01-012016-05-17
http://hdl.handle.net/10256/13198
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.201601396The 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 epoxidationsFinancial 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)
Tots els drets reservats info:eu-repo/semantics/embargoedAccess
Epòxids
Epoxy compounds
Alquens
Alkenes
Ferro
Iron
Exceedingly fast oxygen atom transfer to olefins via a catalytically competent nonheme iron species
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion