Carregant...
Fitxers
Tipus de document
ArticleVersió
Versió acceptadaData de publicació
Tots els drets reservats
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/165417
P-Stereogenic monophosphines with the 2-p-terphenylyl and 1-pyrenyl substituents. Application to Pd and Ru asymmetric catalysis
Títol de la revista
Director/Tutor
ISSN de la revista
Títol del volum
Recurs relacionat
Resum
tThe synthesis of five optically pure P-stereogenic monophosphines of the type PPhArR (Ar = 2-p-terphenylyl (a), 1-pyrenyl (b); R = OMe, Me, i-Pr) is described. The ligands were fully characterisedand the absolute configurations of PPh(1-pyrenyl)R (3b and 5b; R = OMe and Me respectively) wereconfirmed by X-ray diffraction. The complexation of the monophosphines to Pd and Ru organometal-lic units yielded the neutral complexes [PdCl( 3-2-Me-allyl)P] (10-12) and [RuCl2( 6-p-cymene)P](16-18). Complete characterisation, including the crystal structure determination of [RuCl2( 6-p-cymene)(PMePh(2-p-terphenyl))] (17a) is provided. Neutral palladium complexes appeared as mixturesof two diastereomers in solution according to NMR. The synthesis and characterisation of four cationic[Pd( 3-2-Me-allyl)(P)2]PF6(13 and 14) is also described. The application of neutral Pd complexes tocatalytic styrene hydrovinylation afforded moderate conversions, high chemoselectivities (>92%) to 3-phenyl-1-butene and up to 43% ee with precursor 12a. Cationic Pd complexes were tested as catalyticprecursors in allylic substitution of rac-3-acetoxy-1,3-diphenyl-1-propene (rac-I), with the anion ofdimethylmalonate and benzylamine as nucleophiles, obtaining full conversions and up to 80% ee in alkyl-ation and 60% ee in amination with precursor 13a. Finally, ruthenium complexes were used as catalyticprecursors in transfer hydrogenation of acetophenone, with complete conversions after several hoursbut low enantioselectivities.
Matèries (anglès)
Citació
Citació
CLAVERO PUYAL, Pau, GRABULOSA, Arnald, FONT BARDIA, Ma. mercedes, MULLER, G.. P-Stereogenic monophosphines with the 2-p-terphenylyl and 1-pyrenyl substituents. Application to Pd and Ru asymmetric catalysis. _Journal of Molecular Catalysis A-Chemical_. 2014. Vol. 391, núm. 183-190. [consulta: 21 de gener de 2026]. ISSN: 1381-1169. [Disponible a: https://hdl.handle.net/2445/165417]