How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols

Handle URI:
http://hdl.handle.net/10754/550676
Title:
How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols
Authors:
Manzini, Simone; Poater, Albert; Nelson, David J.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Nolan, Steven P.
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. © 2013 The Royal Society of Chemistry.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols 2014, 5 (1):180 Chem. Sci.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Chem. Sci.
Issue Date:
16-Oct-2013
DOI:
10.1039/C3SC52612G
Type:
Article
ISSN:
2041-6520; 2041-6539
Additional Links:
http://xlink.rsc.org/?DOI=C3SC52612G
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorManzini, Simoneen
dc.contributor.authorPoater, Alberten
dc.contributor.authorNelson, David J.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorNolan, Steven P.en
dc.date.accessioned2015-04-26T14:03:14Zen
dc.date.available2015-04-26T14:03:14Zen
dc.date.issued2013-10-16en
dc.identifier.citationHow phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols 2014, 5 (1):180 Chem. Sci.en
dc.identifier.issn2041-6520en
dc.identifier.issn2041-6539en
dc.identifier.doi10.1039/C3SC52612Gen
dc.identifier.urihttp://hdl.handle.net/10754/550676en
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. © 2013 The Royal Society of Chemistry.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://xlink.rsc.org/?DOI=C3SC52612Gen
dc.rightsArchived with thanks to Chem. Sci.This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. http://creativecommons.org/licenses/by/3.0/en
dc.titleHow phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcoholsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChem. Sci.en
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionEaStCHEM, School of Chemistry, University of St. Andrews, Purdie Building, North Haugh, St. Andrews, Fife, UKen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi, Departament de Química, University of Girona, Campus de Montilivi sn, Girona, Spainen
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno, Via Ponte don Melillo, Fisciano I-84084, Italyen
kaust.authorCavallo, Luigien
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