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Oxidant-Free Au(I)-Catalyzed Halide Exchange and Csp2-O Bond Forming Reactions

Au has been demonstrated to mediate a number of organic transformations through the utilization of its π Lewis acid character, Au(I)/Au(III) redox properties or a combination of both. As a result of the high oxidation potential of the Au(I)/Au(III) couple, redox catalysis involving Au typically requires the use of a strong external oxidant. This study demonstrates unusual external oxidant-free Au(I)-catalyzed halide exchange (including fluorination) and Csp2-O bond formation reactions utilizing a model aryl halide macrocyclic substrate. Additionally, the halide exchange and Csp2-O coupling reactivity could also be extrapolated to substrates bearing a single chelating group, providing further insight into the reaction mechanism. This work provides the first examples of external oxidant-free Au(I)-catalyzed carbon-heteroatom cross-coupling reactions

This work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2013-43012-P, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT- 420000-ACT1) and Generalitat de Catalunya (2014 SGR 862)

American Chemical Society (ACS)

Manager: Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Ministerio de Economía y Competitividad (Espanya)
Author: Serra Parareda, Jordi
Whiteoak, Christopher J.
Acuña-Parés, Ferran
Font Molins, Marc
Luis Luis, Josep Maria
Lloret Fillol, Julio
Ribas Salamaña, Xavi
Abstract: Au has been demonstrated to mediate a number of organic transformations through the utilization of its π Lewis acid character, Au(I)/Au(III) redox properties or a combination of both. As a result of the high oxidation potential of the Au(I)/Au(III) couple, redox catalysis involving Au typically requires the use of a strong external oxidant. This study demonstrates unusual external oxidant-free Au(I)-catalyzed halide exchange (including fluorination) and Csp2-O bond formation reactions utilizing a model aryl halide macrocyclic substrate. Additionally, the halide exchange and Csp2-O coupling reactivity could also be extrapolated to substrates bearing a single chelating group, providing further insight into the reaction mechanism. This work provides the first examples of external oxidant-free Au(I)-catalyzed carbon-heteroatom cross-coupling reactions
This work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2013-43012-P, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT- 420000-ACT1) and Generalitat de Catalunya (2014 SGR 862)
Format: application/pdf
Document access: http://hdl.handle.net/10256/12120
Language: eng
Publisher: American Chemical Society (ACS)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.5b08756
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
AGAUR/2014-2016/2014 SGR-862
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/
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
Rights: Tots els drets reservats
Subject: Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Reaccions químiques
Chemical reactions
Catàlisi
Catalysis
Title: Oxidant-Free Au(I)-Catalyzed Halide Exchange and Csp2-O Bond Forming Reactions
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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