Por favor, use este identificador para citar o enlazar a este item:
http://hdl.handle.net/10261/37753
COMPARTIR / EXPORTAR:
SHARE CORE BASE | |
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE | |
Título: | Asymmetric Hydroformylation of Olefins with Rh Catalysts Modified with Chiral Phosphine−Phosphite Ligands |
Autor: | Rubio Moreno, Miguel CSIC; Suárez, Andrés CSIC ORCID; Álvarez, Eleuterio CSIC ORCID ; Bianchini, Claudio; Oberhauser, Werner; Peruzzini, Maurizio; Pizzano, Antonio CSIC ORCID | Palabras clave: | Asymmetric hydroformylation Olefins Phosphine-phosphite Single-crystal X-ray diffraction NMR Oxyphenylene Styrene Xylyl Allyl cyanide Enantioselectivity Naphthyl Axial-equatorial coordination |
Fecha de publicación: | 1-nov-2007 | Editor: | American Chemical Society | Citación: | Organometallics 26(25): 6428-6436 (2007) | Resumen: | Rhodium complexes stabilized by modularly designed chiral phosphine−phosphite ligands (P−OP) have been tested in the asymmetric hydroformylation of styrene, vinyl naphthalenes, and allyl cyanide. Based on single-crystal X-ray diffraction analysis and NMR studies, restricted aryl rotation has been found to characterize ligands 1e and 1f. The outcome of the rhodium-catalyzed hydroformylation reactions is highly dependent on the nature of the two coordinating functions of the phosphine−phosphite and of the ligand backbone as well. Among the ligands studied, those with an oxyphenylene backbone and PAr2 ends gave the best results, outperforming those with P-stereogenic phosphine groups. The 1-naphthyl-substituted catalyst brought about the hydroformylation of styrene with a 71% ee, while the xylyl catalyst afforded the best results in the hydroformylation of allyl cyanide, yielding an iso/n ratio of 13 and 53% ee in the branched isomer. Several hydrido(carbonyl) species of the formula RhH(CO)2(P−OP) have been generated by reacting Rh(acac)(CO)2/P−OP with syngas. In situ high-pressure NMR experiments showed the phosphine group to occupy an apical position of the trigonal bipyramidal coordination geometry, which allows an aryl−aryl interaction between the phosphine substituents and the substrate during the hydroformylation of vinyl arenes. In line with this finding, a remarkable enantioselectivity of 89% ee was obtained with the naphthyl catalyst and 1-vinyl naphthalene as substrate. | Descripción: | 9 páginas, 5 figuras, 4 tablas, esquemas. | Versión del editor: | http://dx.doi.org/10.1021/om700744b | URI: | http://hdl.handle.net/10261/37753 | DOI: | 10.1021/om700744b | ISSN: | 0276-7333 |
Aparece en las colecciones: | (IIQ) Artículos |
Mostrar el registro completo
CORE Recommender
SCOPUSTM
Citations
57
checked on 06-abr-2024
WEB OF SCIENCETM
Citations
54
checked on 26-feb-2024
Page view(s)
344
checked on 19-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.