Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality

Ross A. Arthurs, Muhammad Ismail, Christopher C. Prior, Vasily S. Oganesyan, Peter N. Horton, Simon J. Coles, Christopher J. Richards

Research output: Contribution to journalArticle

19 Citations (Scopus)
6 Downloads (Pure)

Abstract

Reaction of [IrCp*Cl-2](2) with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration S-p*,R-Ir*. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration S-c,S-p,R-Ir. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

Original languageEnglish
Pages (from-to)3065-3072
Number of pages8
JournalChemistry - A European Journal
Volume22
Issue number9
Early online date25 Jan 2016
DOIs
Publication statusPublished - 24 Feb 2016

Keywords

  • chirality
  • enantioselectivity
  • ferrocene
  • iridacycle
  • stereoselectivity
  • C-H ACTIVATION
  • CYCLOMANGANATED (ETA(6)-ARENE)TRICARBONYLCHROMIUM COMPLEXES
  • EFFECTIVE CORE POTENTIALS
  • METAL-COMPLEXES
  • TRANSFER HYDROGENATION
  • ASYMMETRIC CATALYSIS
  • MOLECULAR CALCULATIONS
  • REDUCTIVE AMINATION
  • FULVENE COMPLEXES
  • LIGAND

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