Expanding the palette of phenanthridinium cations

Andrew G. Cairns, Hans Martin Senn, Michael P. Murphy, Richard C. Hartley

Research output: Contribution to journalArticle

11 Citations (Scopus)
15 Downloads (Pure)

Abstract

5,6-Disubstituted phenanthridinium cations have a range of redox, fluorescence and biological properties. Some properties rely on phenanthridiniums intercalating into DNA, but the use of these cations as exomarkers for the reactive oxygen species (ROS), superoxide, and as inhibitors of acetylcholine esterase (AChE) do not require intercalation. A versatile modular synthesis of 5,6-disubstituted phenanthridiniums that introduces diversity by Suzuki-Miyaura coupling, imine formation and microwave-assisted cyclisation is presented. Computational modelling at the density functional theory (DFT) level reveals that the novel displacement of the aryl halide by an acyclic N-alkylimine proceeds by an SNAr mechanism rather than electrocyclisation. It is found that the displacement of halide is concerted and there is no stable Meisenheimer intermediate, provided the calculations consistently use a polarisable solvent model and a diffuse basis set.

Original languageEnglish
Pages (from-to)3742-3751
Number of pages10
JournalChemistry - A European Journal
Volume20
Issue number13
Early online date19 Feb 2014
DOIs
Publication statusPublished - 24 Mar 2014

Keywords

  • density functional calculations
  • nucleophilic substitution
  • phenanthridinium
  • solvation
  • synthetic methods

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