Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation
Luca Demonti, Daniel Joven‐Sancho, Noel Nebra
Abstract
Abstract Ag III compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement of Ag catalysts in cross‐coupling via 2 e − redox sequences is frequently discarded. Nevertheless, organosilver(III) compounds have been authenticated using tetradentate macrocycles or per fluorinated groups as supporting ligands, and since 2014, first examples of cross‐coupling enabled by Ag I /Ag III redox cycles saw light. This review collects the most relevant contributions to this field, with main focus on aromatic fluorination/ per fluoroalkylation and the identification of Ag III key intermediates. Pertinent comparison between the activity of Ag III R F compounds in aryl‐F and aryl‐CF 3 couplings vs. the one shown by its Cu III R F and Au III R F congeners is herein disclosed, thus providing a more profound picture on the scope of these transformations and the pathways commonly associated to C−R F bond formations enabled by coinage metals.