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Royal Society of Chemistry, Chemical Science, 1(5), p. 180-188

DOI: 10.1039/c3sc52612g

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

Journal article published in 2014 by Simone Manzini, Albert Poater, David J. Nelson ORCID, Luigi Cavallo, Steven P. Nolan ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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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. © 2013 The Royal Society of Chemistry.