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Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings

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

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)

© Journal of Organic Chemistry, 2016, vol. 81, núm. 17, p. 7315-7325

American Chemical Society (ACS)

Manager: Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Ministerio de Ciencia e Innovación (Espanya)
Author: Rovira Coll, Mireia
Soler Vives, Marta
Güell Costa, Imma
Wang, Ming Zheng
Gómez Martín, Laura
Ribas Salamaña, Xavi
Date: 2016 June 1
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
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)
Format: application/pdf
Citation: 025310
ISSN: 0022-3263 (versió paper)
1520-6904 (versió electrònica)
Document access: http://hdl.handle.net/10256/13206
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MINECO/PE 2014-2016/CTQ2013-43012-P
AGAUR/2014-2016/2014 SGR-862
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/acs.joc.6b01035
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/277801
Is part of: © Journal of Organic Chemistry, 2016, vol. 81, núm. 17, p. 7315-7325
Rights: Tots els drets reservats
Subject: Catalitzadors de coure
Copper catalysts
Catàlisi
Catalysis
Reaccions químiques
Chemical reactions
Title: Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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