Mechanochemical arylative detrifluoromethylation of trifluoromethylarenes?

Organic & Biomolecular Chemistry Pub Date: 2023-07-26 DOI: 10.1039/D3OB00787A

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.

Graphical abstract: Mechanochemical arylative detrifluoromethylation of trifluoromethylarenes
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