Expanding the palette of phenanthridinium cations

Cairns, A. G., Senn, H. M. , Murphy, M. P. and Hartley, R. C. (2014) Expanding the palette of phenanthridinium cations. Chemistry: A European Journal, 20(13), pp. 3742-3751. (doi: 10.1002/chem.201304241) (PMID:24677631) (PMCID:PMC4164275)

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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.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Senn, Dr Hans and Hartley, Professor Richard
Authors: Cairns, A. G., Senn, H. M., Murphy, M. P., and Hartley, R. C.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Publisher:Wiley-VCH Verlag
ISSN (Online):1521-3765
Copyright Holders:Copyright © 2014 The Authors
First Published:First published in Chemistry: A European Journal 20(13):3742-3751
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
553931Developing chemical mass spectrometry probes to assess the production of reactive oxygen species in vivoRichard HartleyBiotechnology and Biological Sciences Research Council (BBSRC)BB/I012826/1CHEM - CHEMISTRY