Mechanochemical arylative detrifluoromethylation of trifluoromethylarenes

The stoichiometric defluorinative functionalization of ArCF₃ is a conceptually appealing research target. It enables the challenging late-stage functionalization of CF₃-containing aromatic molecules and contributes to the remedy of environmental risks resulting from the accumulation of relatively inert ArCF₃-containing molecules. Similarly, Ar-CN bond features limit their utilization in cross-coupling reactions. Thus, the employment of benzonitriles in decyanative Suzuki-Miyaura type coupling remains in high demand in the field of C-C bond formation. Herein, we report mechanochemically induced and ytterbium oxide (Yb₂O₃)-mediated defluorinative cyanation of trifluoromethylarenes. In addition, we describe a facile mechanochemically facilitated and nickel-catalyzed decyanative arylation of benzonitriles to access biphenyls. Combining both processes in a one-pot multicomponent protocol to achieve a concise direct arylative detrifluoromethylation of ArCF₃ is described herein. This work is the first hitherto realization of C-C coupling with CF₃ as a formal leaving group.