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Open AccessArticle

Iridium-Catalysed ortho-Directed Deuterium Labelling of Aromatic Esters—An Experimental and Theoretical Study on Directing Group Chemoselectivity

Department of Pure & Applied Chemistry, University of Strathclyde, WestCHEM, 295 Cathedral Street, Glasgow G1 1XL, UK
*
Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Current address: School of Chemistry, University of Edinburgh, EastCHEM, David Brewster Road, Edinburgh EH9 3FJ, UK.
Academic Editor: Michael Findlater
Molecules 2015, 20(7), 11676-11698; https://doi.org/10.3390/molecules200711676
Received: 2 June 2015 / Revised: 17 June 2015 / Accepted: 19 June 2015 / Published: 25 June 2015
(This article belongs to the Special Issue C-H Bond Activation and Functionalization)
Herein we report a combined experimental and theoretical study on the deuterium labelling of benzoate ester derivatives, utilizing our developed iridium N-heterocyclic carbene/phosphine catalysts. A range of benzoate esters were screened, including derivatives with electron-donating and -withdrawing groups in the para- position. The substrate scope, in terms of the alkoxy group, was studied and the nature of the catalyst counter-ion was shown to have a profound effect on the efficiency of isotope exchange. Finally, the observed chemoselectivity was rationalized by rate studies and theoretical calculations, and this insight was applied to the selective labelling of benzoate esters bearing a second directing group. View Full-Text
Keywords: hydrogen isotope exchange; deuterium; iridium; esters; C–H activation; DFT hydrogen isotope exchange; deuterium; iridium; esters; C–H activation; DFT
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MDPI and ACS Style

Devlin, J.; Kerr, W.J.; Lindsay, D.M.; McCabe, T.J.D.; Reid, M.; Tuttle, T. Iridium-Catalysed ortho-Directed Deuterium Labelling of Aromatic Esters—An Experimental and Theoretical Study on Directing Group Chemoselectivity. Molecules 2015, 20, 11676-11698.

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