Deoxygenative Cross‐Coupling of Aromatic Amides with Polyfluoroarenes

• Published in: Angewandte Chemie International Edition Vol. 61; no. 11; pp. e202115497 - n/a
• Main Authors: He, Youliang, Wang, Yuxiao, Li, Shi‐Jun, Lan, Yu, Wang, Xiaoming
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 07.03.2022; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amides; Amines; Carbon; Chemistry; Chemistry, Multidisciplinary; Coupling (molecular); Cross coupling; C−H Functionalization; Deoxygenation; Physical Sciences; Polyfluoroarenes; Polyfluoroarylation; Science & Technology; Structure-function relationships; α-Aminocarbene; alpha-Aminocarbene; ORGANIC-SYNTHESIS; CYCLIZATION CASCADES; C-H Functionalization; Polyfluoroarylation; Amides; SAMARIUM(II) IODIDE; N-HETEROCYCLIC CARBENES; TERTIARY; CHEMOSELECTIVE REDUCTION; ELECTRON-TRANSFER REDUCTION; BOND ACTIVATION; METAL; Polyfluoroarenes; C-H; α-Aminocarbene; C−H Functionalization
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202115497

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. An attractive deoxygenative cross‐coupling of amides with polyfluoroarenes was successfully achieved. Aromatic amides act as readily available carbene precursors through a Sm/SmI2‐mediated deoxygenation process, and the insertion of the carbene into the C−H bond of polyfluoroarene affords architecturally complex and functionally diverse α‐polyfluoroaryl amines in a single step.