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

Molecules

Jennifer Devlin¹  William. J. Kerr¹  David M. Lindsay²  Timothy J. D. McCabe³  Marc Reid¹  Tell Tuttle² 

[1]Department of Pure & Applied Chemistry, University of Strathclyde, WestCHEM, 295 Cathedral Street, Glasgow G1 1XL, UK

[2]

[3]Department of Pure & Applied Chemistry, University of Strathclyde, WestCHEM, 295 Cathedral Street, Glasgow G1 1XL, UK

[4] E-Mails:

关键词: hydrogen isotope exchange;    deuterium;    iridium;    esters;    C–H activation;    DFT;   

DOI  :  10.3390/molecules200711676

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.