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

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Manzini, Simone and Poater, Albert and Nelson, David and Cavallo, Luigi and Nolan, Steven P. (2014) How phenyl makes a difference : mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols. Chemical Science, 5 (1). pp. 180-188. ISSN 2041-6539 (https://doi.org/10.1039/c3sc52612g)

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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.

ORCID iDs

Manzini, Simone, Poater, Albert, Nelson, David ORCID logoORCID: https://orcid.org/0000-0002-9461-5182, Cavallo, Luigi and Nolan, Steven P.;
  • Item type:Article
    ID code:47862
    Dates:
    Date
    Event
    1 January 2014
    Published
    18 October 2013
    Published Online
    Subjects:Science > Chemistry
    Department:UNSPECIFIED
    Depositing user: Pure Administrator
    Date deposited:07 May 2014 10:41
    Last modified:11 Nov 2024 10:41
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/47862
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