How phenyl makes a difference: Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols
dc.contributor.author
dc.date.accessioned
2015-05-05T07:13:35Z
dc.date.available
2015-05-05T07:13:35Z
dc.date.issued
2014
dc.identifier.issn
2041-6520
dc.identifier.uri
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.description.sponsorship
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)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation
info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c3sc52612g
dc.relation.ispartof
© Chemical Science, 2014, vol. 5, p. 180-188
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Reconeixement 3.0 Espanya
dc.rights.uri
dc.subject
dc.title
How phenyl makes a difference: Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
Cap
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
020510
dc.contributor.funder
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
2041-6539