Cargando…

C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions

An assessment of the C−H activation catalyst [(COD)Ir(IMes)(PPh(3))]PF(6) (COD=1,5‐cyclooctadiene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear ord...

Descripción completa

Detalles Bibliográficos
Autores principales: Valero, Mégane, Kruissink, Thomas, Blass, Jennifer, Weck, Remo, Güssregen, Stefan, Plowright, Alleyn T., Derdau, Volker
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7232431/
https://www.ncbi.nlm.nih.gov/pubmed/31917506
http://dx.doi.org/10.1002/anie.201914220
Descripción
Sumario:An assessment of the C−H activation catalyst [(COD)Ir(IMes)(PPh(3))]PF(6) (COD=1,5‐cyclooctadiene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear order of the directing groups in the hydrogen isotope exchange (HIE) with an iridium (I) catalyst. Through DFT calculations the iridium–substrate coordination complex has been identified to be the main trigger for reactivity and selectivity in the competition situation with two or more directing groups. We postulate that the competition concept found in this HIE reaction can be used to explain regioselectivities in other transition‐metal‐catalyzed functionalization reactions of complex drug‐type molecules as long as a C−H activation mechanism is involved.