How phenyl makes a difference : mechanistic insights into the ruthenium(II)-catalysed isomerisation of allylic alcohols
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[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.
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 , vol 5 , no. 1 , pp. 180-189 . DOI: 10.1039/C3SC52612G
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