Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines

[{Rh(μ-Cl)(H)2(IPr)}2] (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazole-2-ylidene) was found to be an efficient catalyst for the synthesis of novel propargylamines by a one-pot three-component reaction between primary arylamines, aliphatic aldehydes, and triisopropylsilylacetylene. This methodology o...

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Detalles Bibliográficos
Autores: Rubio-Pérez, Laura, Iglesias, Manuel, Munárriz, Julen, Polo, Víctor, Pérez-Torrente, Jesús J., Oro, Luis A.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/133799
Acceso en línea:http://hdl.handle.net/10261/133799
Access Level:acceso abierto
Palabra clave:C-H activation
Multicomponent reactions
Hydroalkynylation
Propargylamines
Rrhodium
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spelling Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylaminesRubio-Pérez, LauraIglesias, ManuelMunárriz, JulenPolo, VíctorPérez-Torrente, Jesús J.Oro, Luis A.C-H activationMulticomponent reactionsHydroalkynylationPropargylaminesRrhodium[{Rh(μ-Cl)(H)2(IPr)}2] (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazole-2-ylidene) was found to be an efficient catalyst for the synthesis of novel propargylamines by a one-pot three-component reaction between primary arylamines, aliphatic aldehydes, and triisopropylsilylacetylene. This methodology offers an efficient synthetic pathway for the preparation of secondary propargylamines derived from aliphatic aldehydes. The reactivity of [{Rh(μ-Cl)(H)2(IPr)}2] with amines and aldehydes was studied, leading to the identification of complexes [RhCl(CO)IPr(MesNH2)] (MesNH2 = 2,4,6-trimethylaniline) and [RhCl(CO)2IPr]. The latter shows a very low catalytic activity while the former brought about reaction rates similar to those obtained with [{Rh(μ-Cl)(H)2(IPr)}2]. Besides, complex [RhCl(CO)IPr(MesNH2)] reacts with an excess of amine and aldehyde to give [RhCl(CO)IPr{MesN[DOUBLE BOND]CHCH2CH(CH3)2}], which was postulated as the active species. A mechanism that clarifies the scarcely studied catalytic cycle of A3-coupling reactions is proposed based on reactivity studies and DFT calculations.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) (CONSOLIDER INGENIO CSD2009-0050, CTQ2011-27593, CTQ2012-35665 and CTQ2013-42532-P projects) and the DGA/FSE-E07. The support from KFUPM-University of Zaragoza research agreement and the Centre of Research Excellence in Petroleum Refining & KFUPM is gratefully acknowledged. V. P. thankfully acknowledges the resources from the supercomputer >Memento>, technical expertise and assistance provided by BIFI-ZCAM (Universidad de Zaragoza). L.R.-P thanks to CONACyT for a postdoctoral fellowship (204033).Peer ReviewedWiley-VCHConsejo Nacional de Ciencia y Tecnología (México)King Fahd University of Petroleum and MineralsUniversidad de ZaragozaMinisterio de Economía y Competitividad (España)Diputación General de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2016201620152016info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/133799reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-42532-Phttp://dx.doi.org/10.1002/chem.201502993Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1337992026-05-22T06:33:51Z
dc.title.none.fl_str_mv Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
title Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
spellingShingle Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
Rubio-Pérez, Laura
C-H activation
Multicomponent reactions
Hydroalkynylation
Propargylamines
Rrhodium
title_short Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
title_full Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
title_fullStr Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
title_full_unstemmed Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
title_sort Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines
dc.creator.none.fl_str_mv Rubio-Pérez, Laura
Iglesias, Manuel
Munárriz, Julen
Polo, Víctor
Pérez-Torrente, Jesús J.
Oro, Luis A.
author Rubio-Pérez, Laura
author_facet Rubio-Pérez, Laura
Iglesias, Manuel
Munárriz, Julen
Polo, Víctor
Pérez-Torrente, Jesús J.
Oro, Luis A.
author_role author
author2 Iglesias, Manuel
Munárriz, Julen
Polo, Víctor
Pérez-Torrente, Jesús J.
Oro, Luis A.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Consejo Nacional de Ciencia y Tecnología (México)
King Fahd University of Petroleum and Minerals
Universidad de Zaragoza
Ministerio de Economía y Competitividad (España)
Diputación General de Aragón
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv C-H activation
Multicomponent reactions
Hydroalkynylation
Propargylamines
Rrhodium
topic C-H activation
Multicomponent reactions
Hydroalkynylation
Propargylamines
Rrhodium
description [{Rh(μ-Cl)(H)2(IPr)}2] (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazole-2-ylidene) was found to be an efficient catalyst for the synthesis of novel propargylamines by a one-pot three-component reaction between primary arylamines, aliphatic aldehydes, and triisopropylsilylacetylene. This methodology offers an efficient synthetic pathway for the preparation of secondary propargylamines derived from aliphatic aldehydes. The reactivity of [{Rh(μ-Cl)(H)2(IPr)}2] with amines and aldehydes was studied, leading to the identification of complexes [RhCl(CO)IPr(MesNH2)] (MesNH2 = 2,4,6-trimethylaniline) and [RhCl(CO)2IPr]. The latter shows a very low catalytic activity while the former brought about reaction rates similar to those obtained with [{Rh(μ-Cl)(H)2(IPr)}2]. Besides, complex [RhCl(CO)IPr(MesNH2)] reacts with an excess of amine and aldehyde to give [RhCl(CO)IPr{MesN[DOUBLE BOND]CHCH2CH(CH3)2}], which was postulated as the active species. A mechanism that clarifies the scarcely studied catalytic cycle of A3-coupling reactions is proposed based on reactivity studies and DFT calculations.
publishDate 2015
dc.date.none.fl_str_mv 2015
2016
2016
2016
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/133799
url http://hdl.handle.net/10261/133799
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-42532-P
http://dx.doi.org/10.1002/chem.201502993
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.811543

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