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dc.contributor.authorHashmi, A. Stephen K
dc.contributor.authorSchuster, Andreas M.
dc.contributor.authorGaillard, Sylvain
dc.contributor.authorCavallo, Luigi
dc.contributor.authorPoater, Albert
dc.contributor.authorNolan, Steven P.
dc.date.accessioned2015-08-03T09:34:22Z
dc.date.available2015-08-03T09:34:22Z
dc.date.issued2011-11-28
dc.identifier.citationHashmi, A. S. K., Schuster, A. M., Gaillard, S., Cavallo, L., Poater, A., & Nolan, S. P. (2011). Selectivity Switch in the Synthesis of Vinylgold(I) Intermediates. Organometallics, 30(22), 6328–6337. doi:10.1021/om2009556
dc.identifier.issn02767333
dc.identifier.doi10.1021/om2009556
dc.identifier.urihttp://hdl.handle.net/10754/561930
dc.description.abstractAn unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.
dc.description.sponsorshipThe ERC (FUNCAT to SPN) and the EPSRC are gratefully acknowledged for support of this work. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-04170). Umicore AG and Chemetall AG are thanked for their generous gifts of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder. We thank Dr. Pierrick Nun for valuable discussions.
dc.publisherAmerican Chemical Society (ACS)
dc.titleSelectivity switch in the synthesis of vinylgold(I) intermediates
dc.typeArticle
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Division
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalOrganometallics
dc.contributor.institutionOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
dc.contributor.institutionEaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, United Kingdom
dc.contributor.institutionLaboratoire de Chimie Moléculaire et Thioorganique, UMR 6507, Université de Caen, 6 bd. Maréchal Juin, 14050 Caen, France
dc.contributor.institutionDipartimento di Chimica, Università di Salerno, Via ponte don Melillo, 84084 Fisciano, Italy
dc.contributor.institutionCatalan Institute for Water Research (ICRA), Scientific and Technological Park, University of Girona, Emili Grahit 101, E-17003 Girona, Spain
kaust.personCavallo, Luigi


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