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

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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.
Original languageEnglish
Pages (from-to)11676-11698
Number of pages23
JournalMolecules
Volume20
Issue number7
DOIs
Publication statusPublished - 25 Jun 2015

Fingerprint

Iridium
Deuterium
Benzoates
iridium
Labeling
marking
esters
deuterium
Esters
phosphine
Theoretical Models
Bearings (structural)
Derivatives
catalysts
Catalysts
Radiation counters
carbenes
phosphines
Isotopes
counters

Keywords

  • hydrogen isotope exchange
  • deuterium
  • iridium
  • esters
  • C-H activation
  • DFT

Cite this

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title = "Iridium-catalysed ortho-directed deuterium labelling of aromatic esters – an experimental and theoretical study on directing group chemoselectivity",
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.",
keywords = "hydrogen isotope exchange, deuterium, iridium, esters, C-H activation, DFT",
author = "Jennifer Devlin and Kerr, {William J.} and Lindsay, {David M.} and McCabe, {Timothy J.D.} and Marc Reid and Tell Tuttle",
year = "2015",
month = "6",
day = "25",
doi = "10.3390/molecules200711676",
language = "English",
volume = "20",
pages = "11676--11698",
journal = "Molecules",
issn = "1420-3049",
number = "7",

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TY - JOUR

T1 - Iridium-catalysed ortho-directed deuterium labelling of aromatic esters – an experimental and theoretical study on directing group chemoselectivity

AU - Devlin, Jennifer

AU - Kerr, William J.

AU - Lindsay, David M.

AU - McCabe, Timothy J.D.

AU - Reid, Marc

AU - Tuttle, Tell

PY - 2015/6/25

Y1 - 2015/6/25

N2 - 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.

AB - 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.

KW - hydrogen isotope exchange

KW - deuterium

KW - iridium

KW - esters

KW - C-H activation

KW - DFT

UR - http://www.mdpi.com/journal/molecules

U2 - 10.3390/molecules200711676

DO - 10.3390/molecules200711676

M3 - Article

VL - 20

SP - 11676

EP - 11698

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 7

ER -