Título:
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How phenyl makes a difference : Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols
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Autor/a:
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Manzini, Simone; Poater Teixidor, Albert; Nelson, David J.; Cavallo, Luigi; Nolan, Steven P.
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Abstract:
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[RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols |
Abstract:
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We thank the ERC (Advanced Investigator Award ` FUNCAT' to SPN) and the EPSRC for funding. Umicore is thanked for gi. s of materials. SPN is a Royal Society Wolfson Merit Award holder. Melanja Smith and Dr Tomas Lebl are thanked for assistance with NMR spectroscopy facilities. Dr Cesar A. Urbina-Blanco is acknowledged for useful discussions. LC thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900) |
Materia(s):
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-Isomerització -Isomerization -Ruteni -Ruthenium -Mecanismes de reacció (Química) -Reaction mechanisms (Chemistry) -Funcional de densitat, Teoria del -Density functionals -Catalitzadors -Catalysts |
Derechos:
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Reconeixement 3.0 Espanya
http://creativecommons.org/licenses/by/3.0/es/deed.ca |
Tipo de documento:
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Artículo Artículo - Versión publicada |
Editor:
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Royal Society of Chemistry (RSC)
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