New Vistas in Transmetalation with Discrete “AgCF3” Species: Implications in Pd‐Mediated Trifluoromethylation Reactions

This work describes the employment of discrete “AgCF3” complexes as efficient transmetalating agents to PdII to surmount overlooked challenges related to the transmetalation step in Pd‐catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF3)2] complex, under stoichiometric and catalytic conditions, in the unprecedented one‐pot formation of PhCF3 using PhI as starting material. Moreover, we show that the transmetalation step, which is often ignored in these transformations, can also determine the success or failure of the coupling process. Being for the benefit of trifluoromethylation! Disclosed here is the potential of [LAgCF3] and (Cat)[Ag(CF3)2] as CF3 shuttles to PdII, in the context of one of the hidden challenges in trifluoromethylation processes, the transmetalation step.