Selectivity switch in the synthesis of vinylgold(I) intermediates

Handle URI:
http://hdl.handle.net/10754/561930
Title:
Selectivity switch in the synthesis of vinylgold(I) intermediates
Authors:
Hashmi, A. Stephen K; Schuster, Andreas M.; Gaillard, Sylvain; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Poater, Albert; Nolan, Steven P.
Abstract:
An 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.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
28-Nov-2011
DOI:
10.1021/om2009556
Type:
Article
ISSN:
02767333
Sponsors:
The 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.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorHashmi, A. Stephen Ken
dc.contributor.authorSchuster, Andreas M.en
dc.contributor.authorGaillard, Sylvainen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorPoater, Alberten
dc.contributor.authorNolan, Steven P.en
dc.date.accessioned2015-08-03T09:34:22Zen
dc.date.available2015-08-03T09:34:22Zen
dc.date.issued2011-11-28en
dc.identifier.issn02767333en
dc.identifier.doi10.1021/om2009556en
dc.identifier.urihttp://hdl.handle.net/10754/561930en
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.en
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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleSelectivity switch in the synthesis of vinylgold(I) intermediatesen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germanyen
dc.contributor.institutionEaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, United Kingdomen
dc.contributor.institutionLaboratoire de Chimie Moléculaire et Thioorganique, UMR 6507, Université de Caen, 6 bd. Maréchal Juin, 14050 Caen, Franceen
dc.contributor.institutionDipartimento di Chimica, Università di Salerno, Via ponte don Melillo, 84084 Fisciano, Italyen
dc.contributor.institutionCatalan Institute for Water Research (ICRA), Scientific and Technological Park, University of Girona, Emili Grahit 101, E-17003 Girona, Spainen
kaust.authorCavallo, Luigien
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