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

Simone Manzini, Albert Poater, David Nelson, Luigi Cavallo, Steven P. Nolan

Research output: Contribution to journalArticle

47 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)180-188
Number of pages9
JournalChemical Science
Volume5
Issue number1
Early online date18 Oct 2013
DOIs
Publication statusPublished - 1 Jan 2014
Externally publishedYes

Keywords

  • primary allylic alcohols
  • ketones
  • phenyl

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