Direct 2,2,2‐Trifluoro and 2,2‐Difluoroethoxylation of a Model Macrocyclic Ar−H Substrate via Ni‐Catalysis

Autor: Lorena Capdevila, Max T. G. M. Derks, Marc Montilla, Josep M. Luis, Jana Roithová, Xavi Ribas
Jazyk: angličtina
Rok vydání: 2024
Předmět:
Zdroj: ChemistryEurope, Vol 2, Iss 5, Pp n/a-n/a (2024)
Druh dokumentu: article
ISSN: 2751-4765
DOI: 10.1002/ceur.202400023
Popis: Abstract Herein, we describe the trifluoro‐ and difluoroethoxylation of C(sp2)‐H bonds using nickel(II) complexes incorporating a model macrocyclic arene substrate. Due to the coordinative properties of the macrocyclic substrate, we were able to detect and characterize the just‐formed C(sp2)−OCH2CF3−Ni(II) species by HRMS and IRPD. DFT studies on the C(sp2)−OCH2CF3 bond formation mechanism indicate that it involves a Ni(III)/Ni(I) reductive elimination followed by oxidation to Ni(II) rather than the higher energy barrier Ni(IV)/Ni(II) reductive elimination. This mechanistic investigation deepens the versatile redox abilities of Ni compounds and might help in designing new catalysts for the 2,2,2‐trifluoroethoxylation and 2,2‐difluoroethoxylation of arene C−H bonds.
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