Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Abstract

AbstractAgIII compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement of Ag catalysts in cross‐coupling via 2e− redox sequences is frequently discarded. Nevertheless, organosilver(III) compounds have been authenticated using tetradentate macrocycles or perfluorinated groups as supporting ligands, and since 2014, first examples of cross‐coupling enabled by AgI/AgIII redox cycles saw light. This review collects the most relevant contributions to this field, with main focus on aromatic fluorination/perfluoroalkylation and the identification of AgIII key intermediates. Pertinent comparison between the activity of AgIIIRF compounds in aryl‐F and aryl‐CF3 couplings vs. the one shown by its CuIIIRF and AuIIIRF congeners is herein disclosed, thus providing a more profound picture on the scope of these transformations and the pathways commonly associated to C−RF bond formations enabled by coinage metals.