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Issue 1, 2014
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How phenyl makes a difference: mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols

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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.

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

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Publication details

The article was received on 17 Sep 2013, accepted on 16 Oct 2013 and first published on 18 Oct 2013


Article type: Edge Article
DOI: 10.1039/C3SC52612G
Chem. Sci., 2014,5, 180-188
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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

    S. Manzini, A. Poater, D. J. Nelson, L. Cavallo and S. P. Nolan, Chem. Sci., 2014, 5, 180
    DOI: 10.1039/C3SC52612G

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