Deoxygenative Cross‐Coupling of Aromatic Amides with Polyfluoroarenes.

Considering the ubiquitous nature and ready synthesis of amides, and the great significance of organofluorine‐containing species, the cross‐coupling of amides and polyfluoroarenes, leading to new carbon–carbon bond‐forming methodologies, would find useful applications in synthesis, late‐stage functionalization, and rapid generation of molecular diversity. Herein, we present a novel synthesis of α‐polyfluoroaryl amines via Sm/SmI2‐mediated deoxygenative cross‐coupling of aromatic amides with polyfluoroarenes through direct C−H functionalization. The structural and functional diversity of these readily available precursors provides a versatile and flexible strategy for the streamlined synthesis of α‐polyfluoroaryl amines. Combining experimental and theoretical studies, a novel plausible mechanism of the α‐aminocarbene‐mediated C−H insertion has been revealed, which may stimulate future work for the development of novel methods in amine synthesis. [ABSTRACT FROM AUTHOR]