On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

Handle URI:
http://hdl.handle.net/10754/621705
Title:
On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes
Authors:
Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Martin, Anthony R.; Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Nelson, David J.; Cordes, David B.; Slawin, Alexandra M. Z.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Nolan, Steven P.; Poater, Albert
Abstract:
Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Gómez-Suárez A, Oonishi Y, Martin AR, Vummaleti SVC, Nelson DJ, et al. (2015) On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes. Chem Eur J 22: 1125–1132. Available: http://dx.doi.org/10.1002/chem.201503097.
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
13-Dec-2015
DOI:
10.1002/chem.201503097
Type:
Article
ISSN:
0947-6539
Sponsors:
The ERC (Advanced Investigator Award-FUNCAT), EPSRC, and Syngenta are gratefully acknowledged for support. Umicore AG is acknowledged for their generous gift of materials. S.P.N. and L.C. thank the King Abdullah University of Science and Technology (CCF project) for support. Y.O. thanks the Uehara Memorial Foundation for a Research Fellowship. A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).
Is Supplemented By:
Gómez-Suárez, A., Oonishi, Y., Martin, A. R., Vummaleti, S. V. C., Nelson, D. J., Cordes, D. B., … Poater, A. (2016). CCDC 1030163: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc13kz2q; DOI:10.5517/ccdc.csd.cc13kz2q; HANDLE:http://hdl.handle.net/10754/624495
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/chem.201503097/full
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGómez-Suárez, Adriánen
dc.contributor.authorOonishi, Yoshihiroen
dc.contributor.authorMartin, Anthony R.en
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorNelson, David J.en
dc.contributor.authorCordes, David B.en
dc.contributor.authorSlawin, Alexandra M. Z.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorPoater, Alberten
dc.date.accessioned2016-11-03T13:23:10Z-
dc.date.available2016-11-03T13:23:10Z-
dc.date.issued2015-12-13en
dc.identifier.citationGómez-Suárez A, Oonishi Y, Martin AR, Vummaleti SVC, Nelson DJ, et al. (2015) On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes. Chem Eur J 22: 1125–1132. Available: http://dx.doi.org/10.1002/chem.201503097.en
dc.identifier.issn0947-6539en
dc.identifier.doi10.1002/chem.201503097en
dc.identifier.urihttp://hdl.handle.net/10754/621705-
dc.description.abstractHerein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.description.sponsorshipThe ERC (Advanced Investigator Award-FUNCAT), EPSRC, and Syngenta are gratefully acknowledged for support. Umicore AG is acknowledged for their generous gift of materials. S.P.N. and L.C. thank the King Abdullah University of Science and Technology (CCF project) for support. Y.O. thanks the Uehara Memorial Foundation for a Research Fellowship. A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/chem.201503097/fullen
dc.subjectAlkynesen
dc.subjectDensity functional calculationsen
dc.subjectGolden
dc.subjectHomogeneous catalysisen
dc.subjectHydrophenoxylationen
dc.subjectReaction mechanismsen
dc.titleOn the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionEaStCHEM School of Chemistry; University of St. Andrews; North Haugh St. Andrews, Fife KY16 9ST UKen
dc.contributor.institutionFaculty of Pharmaceutical Sciences; Hokkaido University; Sapporo 060-0812 Japanen
dc.contributor.institutionInstitut de Chimie de Nice; UMR 7272; Université de Nice Sophia Antipolis, CNRS; Parc Valrose 06108 Nice cedex 2 Franceen
dc.contributor.institutionWestCHEM Department of Pure & Applied Chemistry; University of Strathclyde, Thomas Graham Building; 295 Cathedral Street Glasgow G1 1XL UKen
dc.contributor.institutionChemistry Department; College of Science; King Saud University; P.O. Box 2455 Riyadh 11451 Saudi Arabiaen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química; Universitat de Girona; Campus Montilivi 17071 Girona, Catalonia Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByGómez-Suárez, A., Oonishi, Y., Martin, A. R., Vummaleti, S. V. C., Nelson, D. J., Cordes, D. B., … Poater, A. (2016). CCDC 1030163: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc13kz2qen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc13kz2qen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624495en
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