Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

Handle URI:
http://hdl.handle.net/10754/563538
Title:
Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes
Authors:
Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Falivene, Laura; Poater, Albert; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
2-May-2014
DOI:
10.1021/cs5001575
Type:
Article
ISSN:
21555435
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorPoater, Alberten
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T11:53:57Zen
dc.date.available2015-08-03T11:53:57Zen
dc.date.issued2014-05-02en
dc.identifier.issn21555435en
dc.identifier.doi10.1021/cs5001575en
dc.identifier.urihttp://hdl.handle.net/10754/563538en
dc.description.abstractWe demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.en
dc.publisherAmerican Chemical Society (ACS)en
dc.subjectab initio molecular dynamicsen
dc.subjectdensity functional theoryen
dc.subjectgold catalysisen
dc.subjectmesoionic carbeneen
dc.subjectthermodynamic and kinetic controlen
dc.titleDeconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalACS Catalysisen
dc.contributor.institutionDipartimento di Chimica e Biologia, Universita di Salerno, Via Giovanni Paolo II, 84084 Fisciano, Italyen
dc.contributor.institutionInstitut de Química Computacional i Catalisi, Departament de Química, Campus Montilivi, 17071 Girona, Catalonia, Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
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