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dc.contributor.authorVummaleti, Sai V. C.
dc.contributor.authorAlghamdi, Miasser
dc.contributor.authorPoater, Albert
dc.contributor.authorFalivene, Laura
dc.contributor.authorScaranto, Jessica
dc.contributor.authorBeetstra, Dirk J.
dc.contributor.authorMorton, Jason G.
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2016-11-03T13:23:06Z
dc.date.available2016-11-03T13:23:06Z
dc.date.issued2015-11-13
dc.identifier.citationVummaleti SVC, Al-Ghamdi M, Poater A, Falivene L, Scaranto J, et al. (2015) Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations. Organometallics 34: 5549–5554. Available: http://dx.doi.org/10.1021/acs.organomet.5b00749.
dc.identifier.issn0276-7333
dc.identifier.issn1520-6041
dc.identifier.doi10.1021/acs.organomet.5b00749
dc.identifier.urihttp://hdl.handle.net/10754/621702
dc.description.abstractDensity functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.
dc.description.sponsorshipEuropean Commission[CIG09-GA-2011-293900]
dc.description.sponsorshipMinisterio de Economía y Competitividad[CTQ2014-59832-JIN]
dc.description.sponsorshipKing Abdullah University of Science and Technology
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00749
dc.titleMechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentSABIC - Corporate Research and Innovation Center (CRI) at KAUST
dc.identifier.journalOrganometallics
dc.contributor.institutionInstitut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, Campus Montilivi, Girona, Catalonia, Spain
kaust.personVummaleti, Sai V. C.
kaust.personAl-Ghamdi, Miasser
kaust.personFalivene, Laura
kaust.personScaranto, Jessica
kaust.personBeetstra, Dirk J.
kaust.personMorton, Jason G.
kaust.personCavallo, Luigi
dc.date.published-online2015-11-13
dc.date.published-print2015-12-14


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