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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Detalles Bibliográficos
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
Descripción
Sumario: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.