Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation

An interesting reaction for the synthesis of aromatic carbo- and heterocycles is the transition-metal catalyzed [2 + 2 + 2] cycloaddition reaction. In this elegant and atom-efficient process three C-C or C-X (X = N, O, S...) bonds are formed in a single synthetic process. The [2 + 2 + 2] cycloadditi...

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Detalhes bibliográficos
Autores: Torres Antón, Òscar, Roglans i Ribas, Anna, Pla i Quintana, Anna, Luis Luis, Josep Maria, Solà i Puig, Miquel
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2014
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositório:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/11334
Acesso em linha:http://hdl.handle.net/10256/11334
Access Level:Acesso embargado
Palavra-chave:Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Piridina
Pyridine
Wilkinson, Catalizador de
Wilkinson catalyst
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Ciclització (Química)
Ring formation (Chemistry)
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spelling Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formationTorres Antón, ÒscarRoglans i Ribas, AnnaPla i Quintana, AnnaLuis Luis, Josep MariaSolà i Puig, MiquelReaccions d'addicióAddition reactionsFuncional de densitat, Teoria delDensity functionalsPiridinaPyridineWilkinson, Catalizador deWilkinson catalystMecanismes de reacció (Química)Reaction mechanisms (Chemistry)Ciclització (Química)Ring formation (Chemistry)An interesting reaction for the synthesis of aromatic carbo- and heterocycles is the transition-metal catalyzed [2 + 2 + 2] cycloaddition reaction. In this elegant and atom-efficient process three C-C or C-X (X = N, O, S...) bonds are formed in a single synthetic process. The [2 + 2 + 2] cycloaddition is catalyzed by a variety of organometallic complexes, including more than 15 different metals. In this work, we carry out computational studies of the reaction mechanism between two acetylenes and a nitrile to form substituted pyridines catalyzed by the Wilkinson complex. Our results show that initial oxidative addition between the two acetylene molecules is the rate-determining step. Oxidative addition between two acetylenes is more favorable than between acetylene and nitrile moieties. Our results are in agreement with the experimental finding that the formation of pyridines in some cases requires the use of an excess of nitrile. Nitriles with electron withdrawing substituents favor the incorporation of nitrile in the insertion process and improve the ratio of pyridine vs. benzeneThe following organizations are thanked for financial support: the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-23121 BQU), the Generalitat de Catalunya (projects number 2009SGR637, Xarxa de Referencia en Quimica Teorica i Computacional, and Fl PhD fellowship to O.T.), and the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003. Support for the research of M. S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de CatalunyaElsevierMinisterio de Ciencia e Innovación (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de RecercaGeneralitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfoinfo2014info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/11334http://hdl.handle.net/10256/11334© Journal of Organometallic Chemistry, 2014, vol. 768, p. 15-22Articles 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/10.1016/j.jorganchem.2014.06.014info:eu-repo/semantics/altIdentifier/issn/0022-328Xinfo:eu-repo/grantAgreement/MICINN//CTQ2011-23121info:eu-repo/grantAgreement/MICINN//CTQ2011-23156AGAUR/2009-2014/2009 SGR-637AGAUR/2009-2014/2009 SGR-637Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/113342026-05-29T05:05:01Z
dc.title.none.fl_str_mv Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
title Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
spellingShingle Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
Torres Antón, Òscar
Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Piridina
Pyridine
Wilkinson, Catalizador de
Wilkinson catalyst
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Ciclització (Química)
Ring formation (Chemistry)
title_short Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
title_full Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
title_fullStr Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
title_full_unstemmed Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
title_sort Computational insight into Wilkinson's complex catalyzed [2 + 2 + 2] cycloaddition mechanism leading to pyridine formation
dc.creator.none.fl_str_mv Torres Antón, Òscar
Roglans i Ribas, Anna
Pla i Quintana, Anna
Luis Luis, Josep Maria
Solà i Puig, Miquel
author Torres Antón, Òscar
author_facet Torres Antón, Òscar
Roglans i Ribas, Anna
Pla i Quintana, Anna
Luis Luis, Josep Maria
Solà i Puig, Miquel
author_role author
author2 Roglans i Ribas, Anna
Pla i Quintana, Anna
Luis Luis, Josep Maria
Solà i Puig, Miquel
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
dc.subject.none.fl_str_mv Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Piridina
Pyridine
Wilkinson, Catalizador de
Wilkinson catalyst
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Ciclització (Química)
Ring formation (Chemistry)
topic Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Piridina
Pyridine
Wilkinson, Catalizador de
Wilkinson catalyst
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Ciclització (Química)
Ring formation (Chemistry)
description An interesting reaction for the synthesis of aromatic carbo- and heterocycles is the transition-metal catalyzed [2 + 2 + 2] cycloaddition reaction. In this elegant and atom-efficient process three C-C or C-X (X = N, O, S...) bonds are formed in a single synthetic process. The [2 + 2 + 2] cycloaddition is catalyzed by a variety of organometallic complexes, including more than 15 different metals. In this work, we carry out computational studies of the reaction mechanism between two acetylenes and a nitrile to form substituted pyridines catalyzed by the Wilkinson complex. Our results show that initial oxidative addition between the two acetylene molecules is the rate-determining step. Oxidative addition between two acetylenes is more favorable than between acetylene and nitrile moieties. Our results are in agreement with the experimental finding that the formation of pyridines in some cases requires the use of an excess of nitrile. Nitriles with electron withdrawing substituents favor the incorporation of nitrile in the insertion process and improve the ratio of pyridine vs. benzene
publishDate 2014
dc.date.none.fl_str_mv 2014
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/10256/11334
http://hdl.handle.net/10256/11334
url http://hdl.handle.net/10256/11334
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2014.06.014
info:eu-repo/semantics/altIdentifier/issn/0022-328X
info:eu-repo/grantAgreement/MICINN//CTQ2011-23121
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
AGAUR/2009-2014/2009 SGR-637
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 Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv © Journal of Organometallic Chemistry, 2014, vol. 768, p. 15-22
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 15.811543

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