Iridium-catalysed ortho-directed deuterium labelling of aromatic esters – an experimental and theoretical study on directing group chemoselectivity

Devlin, Jennifer and Kerr, William J. and Lindsay, David M. and McCabe, Timothy J.D. and Reid, Marc and Tuttle, Tell (2015) Iridium-catalysed ortho-directed deuterium labelling of aromatic esters – an experimental and theoretical study on directing group chemoselectivity. Molecules, 20 (7). pp. 11676-11698. ISSN 1420-3049 (https://doi.org/10.3390/molecules200711676)

[thumbnail of Devlin-etal-Molecules-2015-Iridium-catalysed-ortho-directed-deuterium-labelling-of-aromatic-esters]
Preview
 Text. Filename: Devlin_etal_Molecules_2015_Iridium_catalysed_ortho_directed_deuterium_labelling_of_aromatic_esters.pdf
Accepted Author Manuscript
Download (1MB)| Preview
[thumbnail of Devlin-etal-Molecules-2015-Iridium-catalysed-ortho-directed-deuterium-labelling-of-aromatic-esters-Supporting-information]
Preview
 Text. Filename: Devlin_etal_Molecules_2015_Iridium_catalysed_ortho_directed_deuterium_labelling_of_aromatic_esters_Supporting_information.pdf
Accepted Author Manuscript
Download (572kB)| Preview

Abstract

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.

CORE (COnnecting REpositories)