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dc.contributor.authorRomero Fructos-Vázquez, Manuel 
dc.contributor.authorBesora, María
dc.contributor.authorBraga, Ataualpa A. C.
dc.contributor.authorDíaz Requejo, María Mar 
dc.contributor.authorMaseras, Feliu
dc.contributor.authorPérez Romero, Pedro José
dc.identifier.citationFructos, M. R., Besora, M., Braga, A. A. C., Díaz-Requejo, M. M., Maseras, F., & Pérez, P. J. (2017). Mechanistic Studies on Gold-Catalyzed Direct Arene C–H Bond Functionalization by Carbene Insertion: The Coinage-Metal Effect. Organometallics, 36(1), 172-179.
dc.identifier.issn1520-6041 (electrónico)
dc.description.abstractThe catalytic functionalization of the Csp 2-H bond of benzene by means of the insertion of the CHCO2Et group from ethyl diazoacetate (N2=CHCO2Et) has been studied with the series of coinage metal complexes IPrMCl (IPr = IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and NaBArF 4 (BArF 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). For Cu and Ag, these examples constitute the first of such metals toward this transformation, that also provides ethyl cyclohepta-2,4,6-trienecarboxylate as by-product from the so-called Buchner reaction. In the case of methyl-substituted benzenes, the reaction exclusively proceeds onto the aromatic ring, the Csp 3-H bond remaining unreacted. A significant coinage metal effect has been observed, since the gold catalyst favors the formation of the insertion product into Csp 2-H bond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studies and theoretical calculations have explained the observed selectivity in terms of the formation of a common Wheland intermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separate routes to each product.es_ES
dc.description.sponsorshipWe thank the Spanish MINECO for CTQ2014-52769-C3-1-R, CTQ2014-57761-R, RED INTECAT CTQ2014-52974-REDC and Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319 and the ICIQ Foundation for financial support.
dc.publisherAmerican Chemical Societyes_ES
dc.rightsAtribución-NoComercial-SinDerivadas 3.0 España*
dc.subject.otherSilver and gold catalysises_ES
dc.subject.otherArene C-H bond functionalizationes_ES
dc.subject.otherCarbene transferes_ES
dc.subject.otherDiazo reagentses_ES
dc.titleMechanistic Studies on Gold-Catalyzed Direct Arene C–H Bond Functionalization by Carbene Insertion: The Coinage-Metal Effectes_ES
dc.relation.projectIDinfo:eu-repo/grantAgreement/Spanish MINECO [CTQ2014-52769-C3-1-R, CTQ2014-57761-R, CTQ2014-52974-REDC, SEV-2013-0319]

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