Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings

We report the Ni-catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a sing...

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Autores: Martín, M. Trinidad, Maya, Celia, Galindo, Agustín, Nicasio, M. Carmen
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/387496
Acceso en línea:http://hdl.handle.net/10261/387496
https://api.elsevier.com/content/abstract/scopus_id/85208959407
Access Level:acceso abierto
Palabra clave:Alkynes
Catalysis
Cycloaddition
Mechanism
Nickel
Phosphines
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spelling Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst LoadingsMartín, M. TrinidadMaya, CeliaGalindo, AgustínNicasio, M. CarmenAlkynesCatalysisCycloadditionMechanismNickelPhosphinesWe report the Ni-catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.We thank financial support from MCIN/AEI/10.13039/501100011033 (Grant PID2020-113797RB-C22). The use of computational resources of the Universidad de Granada (cluster Albaicín) is thankfully acknowledged.Peer reviewedWiley-LissMinisterio de Ciencia e Innovación (España)Universidad de GranadaMartín, M. Trinidad [0000-0003-1682-8374]Maya, Celia [0000-0002-0651-3793]Galindo, Agustín [0000-0002-2772-9171]Nicasio, M. Carmen [0000-0002-6485-2953]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/387496https://api.elsevier.com/content/abstract/scopus_id/85208959407reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113797RB-C22https://doi.org/10.1002/adsc.202400765Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3874962026-05-22T06:33:51Z
dc.title.none.fl_str_mv Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
title Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
spellingShingle Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
Martín, M. Trinidad
Alkynes
Catalysis
Cycloaddition
Mechanism
Nickel
Phosphines
title_short Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
title_full Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
title_fullStr Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
title_full_unstemmed Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
title_sort Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
dc.creator.none.fl_str_mv Martín, M. Trinidad
Maya, Celia
Galindo, Agustín
Nicasio, M. Carmen
author Martín, M. Trinidad
author_facet Martín, M. Trinidad
Maya, Celia
Galindo, Agustín
Nicasio, M. Carmen
author_role author
author2 Maya, Celia
Galindo, Agustín
Nicasio, M. Carmen
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Universidad de Granada
Martín, M. Trinidad [0000-0003-1682-8374]
Maya, Celia [0000-0002-0651-3793]
Galindo, Agustín [0000-0002-2772-9171]
Nicasio, M. Carmen [0000-0002-6485-2953]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Alkynes
Catalysis
Cycloaddition
Mechanism
Nickel
Phosphines
topic Alkynes
Catalysis
Cycloaddition
Mechanism
Nickel
Phosphines
description We report the Ni-catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/387496
https://api.elsevier.com/content/abstract/scopus_id/85208959407
url http://hdl.handle.net/10261/387496
https://api.elsevier.com/content/abstract/scopus_id/85208959407
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/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113797RB-C22
https://doi.org/10.1002/adsc.202400765
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.publisher.none.fl_str_mv Wiley-Liss
publisher.none.fl_str_mv Wiley-Liss
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
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