Aryl-copper(III)-acetylides as key intermediates in Csp2-C sp model couplings under mild conditions
dc.contributor.author
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
dc.identifier.uri
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
info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/
MICINN/PN 2010-2016/CSD2010-00065
AGAUR/2009-2014/2009 SGR-637
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
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
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.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
022116
dc.contributor.funder
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765