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dc.contributor.authorManzini, Simone
dc.contributor.authorPoater, Albert
dc.contributor.authorNelson, David James
dc.contributor.authorCavallo, Luigi
dc.contributor.authorNolan, Steven Patrick
dc.identifier.citationManzini , S , Poater , A , Nelson , D J , Cavallo , L & Nolan , S P 2014 , ' How phenyl makes a difference : mechanistic insights into the ruthenium(II)-catalysed isomerisation of allylic alcohols ' , Chemical Science , vol. 5 , no. 1 , pp. 180-189 .
dc.identifier.otherPURE: 81086749
dc.identifier.otherPURE UUID: a74ba8de-0c66-411d-af5b-1ef5a9eb3862
dc.identifier.otherScopus: 84888610152
dc.identifier.otherWOS: 000327601600021
dc.description.abstract[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.
dc.relation.ispartofChemical Scienceen
dc.rightsCopyright 2014, the Authors. This is an Open Access article licensed under a Creative Commons Attribution 3.0 Unported Licence.en
dc.subjectAllylic alcoholsen
dc.subjectDensity functional theoryen
dc.subjectCatalyst structureen
dc.subjectQD Chemistryen
dc.titleHow phenyl makes a difference : mechanistic insights into the ruthenium(II)-catalysed isomerisation of allylic alcoholsen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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