A Strong cis-Effect in an Imidazole-Imidazolium-Substituted Alkene

Dayne C Georgiou; Mohammad A Haghighatbin; Conor F Hogan; Michael S Scholz; James N Bull; Evan J Bieske; David J D Wilson; Jason L Dutton

doi:10.1002/anie.201702287

A Strong cis-Effect in an Imidazole-Imidazolium-Substituted Alkene

Angew Chem Int Ed Engl. 2017 Jul 10;56(29):8473-8480. doi: 10.1002/anie.201702287. Epub 2017 Apr 21.

Authors

Dayne C Georgiou¹, Mohammad A Haghighatbin¹, Conor F Hogan¹, Michael S Scholz², James N Bull², Evan J Bieske², David J D Wilson¹, Jason L Dutton¹

Affiliations

¹ Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, Victoria, 3086, Australia.
² School of Chemistry, University of Melbourne, Parkville, Victoria, 3010, Australia.

PMID: 28429451
DOI: 10.1002/anie.201702287

Abstract

We report the first example of an alkene with two carbon-bound substituents (imidazole and imidazolium rings) where the Z-isomer has a greater thermodynamic stability than the E-isomer which persists in both the gas phase and in solution. Theoretical calculations, solution fluorescence spectroscopy and gas-phase ion mobility mass spectrometry studies confirm the preference for the Z-isomer, the stability of which is traced to a non-covalent interaction between the imidazole lone pair and the imidazolium ring.

Keywords: E-Z isomerization; cis-effect; conformation analysis; nitrogen heterocycles.

Publication types

Research Support, Non-U.S. Gov't