Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

Density 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-Xant...

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Autores: Vummaleti, Sai Vikrama Chaitanya, Al-Ghamdi, Miasser, Poater Teixidor, Albert, Falivene, Laura, Scaranto, Jessica, Beetstra, Dirk J., Morton, Jason G., Cavallo, Luigi
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/13295
Acceso en línea:http://hdl.handle.net/10256/13295
Access Level:acceso embargado
Palabra clave:Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
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spelling Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene AlkoxyfunctionalizationsVummaleti, Sai Vikrama ChaitanyaAl-Ghamdi, MiasserPoater Teixidor, AlbertFalivene, LauraScaranto, JessicaBeetstra, Dirk J.Morton, Jason G.Cavallo, LuigiFuncional de densitat, Teoria delDensity functionalsMecanismes de reacció (Química)Reaction mechanisms (Chemistry)Density 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 centeA.P. thanks the Spanish MINECO for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)American Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)infoinfo2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/13295http://hdl.handle.net/10256/13295© Organometallics, 2015, vol. 34, núm. 23, p. 5549-5554Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.organomet.5b00749info:eu-repo/semantics/altIdentifier/issn/0276-7333info:eu-repo/semantics/altIdentifier/eissn/1520-6041info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JINinfo:eu-repo/grantAgreement/EC/FP7/293900Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/132952026-05-29T05:05:01Z
dc.title.none.fl_str_mv Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
title Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
spellingShingle Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
Vummaleti, Sai Vikrama Chaitanya
Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
title_short Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
title_full Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
title_fullStr Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
title_full_unstemmed Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
title_sort Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
dc.creator.none.fl_str_mv Vummaleti, Sai Vikrama Chaitanya
Al-Ghamdi, Miasser
Poater Teixidor, Albert
Falivene, Laura
Scaranto, Jessica
Beetstra, Dirk J.
Morton, Jason G.
Cavallo, Luigi
author Vummaleti, Sai Vikrama Chaitanya
author_facet Vummaleti, Sai Vikrama Chaitanya
Al-Ghamdi, Miasser
Poater Teixidor, Albert
Falivene, Laura
Scaranto, Jessica
Beetstra, Dirk J.
Morton, Jason G.
Cavallo, Luigi
author_role author
author2 Al-Ghamdi, Miasser
Poater Teixidor, Albert
Falivene, Laura
Scaranto, Jessica
Beetstra, Dirk J.
Morton, Jason G.
Cavallo, Luigi
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
topic Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
description Density 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 cente
publishDate 2015
dc.date.none.fl_str_mv 2015
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/13295
http://hdl.handle.net/10256/13295
url http://hdl.handle.net/10256/13295
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.organomet.5b00749
info:eu-repo/semantics/altIdentifier/issn/0276-7333
info:eu-repo/semantics/altIdentifier/eissn/1520-6041
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN
info:eu-repo/grantAgreement/EC/FP7/293900
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv © Organometallics, 2015, vol. 34, núm. 23, p. 5549-5554
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.81155

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