Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
dc.contributor.author
dc.date.accessioned
2016-11-22T14:44:14Z
dc.date.available
2016-11-22T14:44:14Z
dc.date.issued
2016-06-01
dc.identifier.issn
0022-3263
dc.identifier.uri
dc.description.abstract
The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms
dc.description.sponsorship
This work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MICINN (CTQ2013-43012-P, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1), and the Catalan DIUE of the Generalitat de Catalunya (2014SGR862)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2013-43012-P/ES/INVESTIGACIONES MECANISTICAS PARA SINTESIS ORGANICA SOSTENIBLE VIA ACTIVACION DE PEQUEÑAS MOLECULAS GASEOSAS Y DE ENLACES C-H CON METALES DE LA PRIMERA SERIE DE TRANSICION/
AGAUR/2014-2016/2014 SGR-862
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/acs.joc.6b01035
dc.relation.ispartof
© Journal of Organic Chemistry, 2016, vol. 81, núm. 17, p. 7315-7325
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
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
025310
dc.contributor.funder
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-6904