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.