Por favor, use este identificador para citar o enlazar a este item:
http://hdl.handle.net/10261/133764
COMPARTIR / EXPORTAR:
SHARE CORE BASE | |
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE | |
Título: | Oxidation and β-alkylation of alcohols catalysed by Iridium(I) complexes with functionalised N-heterocyclic Carbene ligands |
Autor: | Jiménez, M. Victoria CSIC ORCID ; Fernández-Tornos, Javier CSIC; Modrego, Francisco J. CSIC ORCID; Pérez-Torrente, Jesús J. CSIC ORCID; Oro, Luis A. CSIC ORCID | Palabras clave: | N-heterocyclic carbenes Heteroditopic NHC ligands Iridium Alkylation Alcohols Oxidation |
Fecha de publicación: | 2015 | Editor: | Wiley-VCH | Citación: | Chemistry - A European Journal 21(49): 17877-17889 (2015) | Resumen: | The borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for C-C bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)-cyclooctadiene complexes having a NHC ligand with a O- or N-functionalised wingtip efficiently catalysed the oxidation and β-alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex [Ir(NCCH)(cod)(MeIm(2- methoxybenzyl))][BF] (cod=1,5-cyclooctadiene, MeIm=1-methylimidazolyl) having a rigid O-functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF) of 1283 h, and also in the β-alkylation of 2-propanol with butan-1-ol, which gives a conversion of 94 % in 10 h with a selectivity of 99 % for heptan-2-ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross-aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new C-C bond that involves the reaction of an O-bound enolate generated in the basic medium with the electrophilic aldehyde. | Versión del editor: | http://dx.doi.org/10.1002/chem.201502910 | URI: | http://hdl.handle.net/10261/133764 | DOI: | 10.1002/chem.201502910 | Identificadores: | doi: 10.1002/chem.201502910 e-issn: 1521-3765 issn: 0947-6539 |
Aparece en las colecciones: | (ISQCH) Artículos |
Ficheros en este ítem:
Fichero | Descripción | Tamaño | Formato | |
---|---|---|---|---|
Carbene Ligands.pdf | 1,87 MB | Adobe PDF | Visualizar/Abrir |
CORE Recommender
SCOPUSTM
Citations
100
checked on 24-abr-2024
WEB OF SCIENCETM
Citations
98
checked on 22-feb-2024
Page view(s)
244
checked on 23-abr-2024
Download(s)
480
checked on 23-abr-2024
Google ScholarTM
Check
Altmetric
Altmetric
NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.