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. © 2013 The Royal Society of Chemistry.

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Manzini, S., Poater, A., Nelson, D. J., Cavallo, L., & Nolan, S. P. (2014). How phenyl makes a difference: Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols. Chemical Science, 5(1), 180–188. https://doi.org/10.1039/c3sc52612g

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