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研究论文

光激发丰产金属镍催化卤代芳烃与磺酰胺的C(sp2)-N偶联反应

王力卓a, 刘馨忆a, 宋戈洋*,a, 石晓莉a, 薛东*,a   

  1. a胶体与表面教育部重点实验室, 陕西师范大学 化学化工学院 陕西 西安 710119
  • 收稿日期:2025-11-21 修回日期:2025-12-22
  • 基金资助:
    国家自然科学基金(22171174, 22471150, 22402113)、中央高校基本科研业务费(GK202406026, GK202505023, GK202505026)、陕西省创新能力支撑计划(2023-CX-TD-28)、陕西省化学与生物基础科学研究(22JHZ0027)、陕西省自然科学基金(2024JC-YBQN-0075)、天然药物及仿生药物国家重点实验室开放基金(K202437)、陕西省重点研发计划(2024CY-JJQ-26)资助项目.

Photoexcitation-Enabled C-N Coupling of Aryl Halides with Sulfonamides by Earth-Abundant Nickel Catalyst

Lizhuo Wanga, Xinyi Liua, Geyang Song*,a, Xiaoli Shia, Dong Xue*,a   

  1. aSchool of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, Shaanxi 710119, China
  • Received:2025-11-21 Revised:2025-12-22
  • Supported by:
    National Natural Science Foundation of China (22171174, 22471150, 22402113), the Fundamental Research Funds for the Central Universities (GK202406026, GK202505023, GK202505026), the Innovation Capability Support Program of Shaanxi (2023-CX-TD-28), the Fundamental Science Research Project of Shaanxi for Chemistry, Biology (22JHZ0027), the Natural Science Foundation of Shaanxi Province (2024JC-YBQN-0075, 2025JC-YBQN-144), the State Key Laboratory of Natural and Biomimetic Drugs (K202437), and the Key Research and Development Program of Shaanxi (2024CY-JJQ-26) .

磺酰胺类化合物因其丰富的生物活性、独特的反应活性和潜在的药用价值, 在药物化学与合成化学中备受关注. 本文发展了一种无需外加光敏剂的温和高效的方法, 在390-395 nm LED光照下, 实现了丰产金属镍催化卤代芳烃与磺酰胺类化合物的C (sp²) -N偶联反应. 该方法以易得的丰产金属镍为催化剂, 温和可溶性的有机胺作为碱, 无需外加光敏剂, 具有原料易得、反应条件温和、操作简便、底物适用性广、官能团兼容性强等优点, 并可用于生物活性分子的后期修饰. 在克级反应中, 依然能够保持高效的反应产率, 为合成重要的芳基磺酰胺提供了一种可行的替代方案. 机理研究表明, 该反应可能通过NiI-NiIII的催化循环过程.

关键词: 光催化, 镍催化, 芳基卤化物, C-N偶联反应.

Sulfonamide compounds have attracted considerable attention in medicinal and synthetic chemistry due to their diverse biological activities, distinctive reactivity, and potential pharmaceutical value. In this work, a mild and efficient method that requires no external photosensitizer was developed to achieve the C(sp²)-N coupling of aryl halides with sulfonamide compounds under irradiation from 390-395 nm LEDs, catalyzed by an earth-abundant nickel catalyst. The method employs readily available nickel as the catalyst and soluble organic amines as bases, offering advantages such as easily accessible starting materials, mild reaction conditions, simple operation, broad substrate scope, and excellent functional-group tolerance. It can also be applied to late-stage modification of bioactive molecules. Even on the gram scale, the reaction maintains high efficiency and yield, providing a practical alternative route for the synthesis of important aryl sulfonamides. Mechanistic studies suggest that the reaction may proceed through a Ni(I)-Ni(III) catalytic cycle.

Key words: Photocatalysis, Nickel Catalysis, Aryl Halides, C-N Coupling Reaction