Mechanochemical arylative detrifluoromethylation of trifluoromethylarenes

Abstract

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.