高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

光酶催化自由基酰化合成β-酮腈

车福华1,2，白金彤2，黄春帅1,2,3   


  1. 1.安徽中医药大学药学院 2. 烟台新药创制山东省实验室，中科环渤海烟台药物高等研究院 3. 中国科学院上海药物研究所

  • 收稿日期:2026-01-13 修回日期:2026-04-07 网络首发:2026-04-09 发布日期:2026-04-09
  • 通讯作者: 黄春帅 E-mail:huangchunshuai@simm.ac.cn
  • 基金资助:
    国家自然科学基金(批准号: 22407132)资助

Photobiocatalytic Radical Acylation Facilitates the Synthesis of β-Ketonitriles

CHE Fuhua1,2,  BAI Jintong2,  HUANG Chunshuai1,2,3*   

  1. 1. School of Pharmacy, Anhui University of Chinese Medicine, Hefei230012,China; 2. Shandong Laboratory of Yantai Drug Discovery, Bohai Rim Advanced Research Institute for Drug Discovery 3. Shanghai Institute of Materia Medica, Chinese Academy of Sciences
  • Received:2026-01-13 Revised:2026-04-07 Online First:2026-04-09 Published:2026-04-09
  • Contact: Chunshuai Huang E-mail:huangchunshuai@simm.ac.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China (No. 22407132)

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摘要： 本文发展了一种可见光驱动下焦磷酸硫胺素（ThDP）依赖酶与光催化剂协同催化的新方法，实现了芳香醛与偶氮腈的自由基酰化反应，高效合成了一系列β-酮腈类化合物。该体系利用光催化产生氰烷基自由基，并与酶活性中心内由ThDP稳定的酮基自由基发生交叉偶联，在温和条件下构建C–C键。反应具有广泛的底物适用性和良好的官能团兼容性。本研究是首例光生物催化合成β-酮腈的报道，为绿色合成及酶催化非天然转化提供了新策略。

关键词: 光生物催化, 自由基酰化, ThDP, β-酮腈

Abstract: This study reports a novel photobiocatalytic system that integrates thiamine diphosphate (ThDP)-dependent enzymes with photoredox catalysis to achieve radical acylation between aromatic aldehydes and azonitrile reagents under visible light irradiation. This method enables the efficient synthesis of β-ketonitriles via cross-coupling of an enzyme-bound ThDP-derived ketyl radical and a photogenerated cyanoalkyl radical under mild conditions. The reaction exhibits a broad substrate scope and good functional group compatibility. This work represents the first example of synthesizing β-ketonitriles via photobiocatalysis, offering a new strategy for sustainable synthesis and expanding the toolbox for non-natural enzyme catalysis.

Key words: Photobiocatalysis, Radical acylation, ThDP, β-Ketonitriles

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