{ "dc.contributor.author": "Rovira Coll, Mireia" , "dc.contributor.author": "Font Molins, Marc" , "dc.contributor.author": "Acuña-Parés, Ferran" , "dc.contributor.author": "Parella Coll, Teodor" , "dc.contributor.author": "Luis Luis, Josep Maria" , "dc.contributor.author": "Lloret Fillol, Julio" , "dc.contributor.author": "Ribas Salamaña, Xavi" , "dc.date.accessioned": "2015-03-25T10:23:01Z" , "dc.date.available": "2015-03-25T10:23:01Z" , "dc.date.issued": "2014" , "dc.identifier.issn": "0947-6539 (versió paper)" , "dc.identifier.issn": "1521-3765 (versió electrònica)" , "dc.identifier.uri": "http://hdl.handle.net/10256/10204" , "dc.description.abstract": "The mechanism of copper-mediated Sonogashira couplings (so-called Stephens-Castro and Miura couplings) is not well understood and lacks clear comprehension. In this work, the reactivity of a well-defined aryl-Cu III species (1 ClO 4) with p-R-phenylacetylenes (R=NO2, CF3, H) is reported and it is found that facile reductive elimination from a putative aryl-CuIII-acetylide species occurs at room temperature to afford the Caryl - Csp coupling species (IR), which in turn undergo an intramolecular reorganisation to afford final heterocyclic products containing 2H-isoindole (PNO2, PCF3, PHa) or 1,2-dihydroisoquinoline (PHb) substructures. Density Functional Theory (DFT) studies support the postulated reductive elimination pathway that leads to the formation of C sp2-Csp bonds and provide the clue to understand the divergent intramolecular reorganisation when p-H-phenylacetylene is used. Mechanistic insights and the very mild experimental conditions to effect C aryl-Csp coupling in these model systems provide important insights for developing milder copper-catalysed Caryl - C sp coupling reactions with standard substrates in the future" , "dc.description.sponsorship": "We acknowledge financial support from European Research Council for Starting Grant Project ERC-2011-StG-277801 to X. R., MICINN of Spain (INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to X. R., CTQ2012-32436 to T. P., CTQ2012-37420-C02-01/BQU to Dr. M. Costas, RyC contract to J.Ll.-F. and PhD FPI grant to M. F.), Consolider-Ingenio CSD2010-00065, and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637). X. R. thanks an ICREA-Academia award" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "Wiley-VCH Verlag" , "dc.relation": "MINECO/PN 2013-2015/CTQ2012-37420-C02-01" , "dc.relation": "MICINN/PN 2010-2016/CSD2010-00065" , "dc.relation": "AGAUR/2009-2014/2009 SGR-637" , "dc.relation": "MICINN/PN 2011/INP-2011-0059-PCT-420000" , "dc.relation.isformatof": "Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201402711" , "dc.relation.ispartof": "© Chemistry - A European Journal, 2014, vol. 20, p. 10005-10010" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Tots els drets reservats" , "dc.subject": "Compostos organometàl·lics" , "dc.subject": "Organometallic compounds" , "dc.subject": "Coure" , "dc.subject": "Copper" , "dc.subject": "Funcional de densitat, Teoria del" , "dc.subject": "Density functionals" , "dc.subject": "Mecanismes de reacció (Química)" , "dc.subject": "Reaction mechanisms (Chemistry)" , "dc.title": "Aryl-copper(III)-acetylides as key intermediates in Csp2-C sp model couplings under mild conditions" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/embargoedAccess" , "dc.embargo.terms": "Cap" , "dc.relation.projectID": "info:eu-repo/grantAgreement/EC/FP7/277801" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "http://dx.doi.org/10.1002/chem.201402711" , "dc.identifier.idgrec": "022116" , "dc.contributor.funder": "European Research Council" , "dc.contributor.funder": "Ministerio de Ciencia e Innovación (Espanya)" }