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)
|
Text
94338.pdf - Published Version Available under License Creative Commons Attribution. 647kB |
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.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| 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: | 0947-6539 |
| 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 |
University Staff: Request a correction | Enlighten Editors: Update this record
Funder and Project Information
Funder and Project Information