State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2022 Mar 7;61(11):e202115497. doi: 10.1002/anie.202115497. Epub 2022 Jan 27.
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/SmI -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.
考虑到酰胺的普遍存在和易于合成，以及含氟有机化合物的重要性，酰胺与多氟芳烃的交叉偶联将为合成、后期功能化和快速产生分子多样性提供有用的方法。在此，我们通过 Sm/SmI-介导的芳基酰胺与多氟芳烃的脱氧交叉偶联，通过直接 C-H 官能化，提出了一种通过 Sm/SmI-介导的脱氧交叉偶联来合成α-多氟芳基胺的新方法。这些易得前体的结构和功能多样性为α-多氟芳基胺的流线型合成提供了一种通用且灵活的策略。通过实验和理论研究相结合，揭示了一种新颖的α-氨基卡宾介导的 C-H 插入的可能机制，这可能会激发未来在胺合成方面开发新方法的工作。
