Deoxygenative Cross-Coupling of Aromatic Amides with Polyfluoroarenes

Abstract

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.

Keywords: Amides; C−H Functionalization; Polyfluoroarenes; Polyfluoroarylation; α-Aminocarbene.