有机化学 ›› 2022, Vol. 42 ›› Issue (12): 3944-3958.DOI: 10.6023/cjoc202206058 上一篇    下一篇

所属专题: 自由基化学专辑

综述与进展

可见光促进重氮化合物参与的自由基反应

李森, 周磊*()   

  1. 中山大学化学学院 广州 510006
  • 收稿日期:2022-06-30 修回日期:2022-08-16 发布日期:2022-09-23
  • 通讯作者: 周磊
  • 基金资助:
    国家自然科学基金(21871300)

Visible Light-Promoted Radical Reactions of Diazo Compounds

Sen Li, Lei Zhou()   

  1. School of Chemistry, Sun Yat-Sen University, Guangzhou 510006
  • Received:2022-06-30 Revised:2022-08-16 Published:2022-09-23
  • Contact: Lei Zhou
  • Supported by:
    National Natural Science Foundation of China(21871300)

重氮化合物是有机合成的一类重要中间体, 具有丰富多样的化学转化. 在过去几十年, 以重氮化合物为金属卡宾前体的反应已取得了许多重要进展. 与之相反, 关于重氮化合物自由基反应的研究仍然较少. 由于可见光氧化还原催化在温和条件下产生自由基的特性, 将可见光氧化还原催化与重氮化合物结合, 发展出了一些有别于经典卡宾过程的新反应, 进一步拓展了重氮化合物在合成中的应用. 总结了近五年来可见光促进重氮化合物参与自由基反应的进展, 包括: (1)重氮化合物作为亲核试剂的反应, (2)重氮化合物作为卡拜等价物前体的反应, (3)重氮化合物作为自由基受体的反应, (4)重氮化合物作为自由基前体的反应. 对反应机理的详尽分析, 也有助于读者能更深入地了解重氮化合物参与自由基反应及相关可见光化学的基本特性.

关键词: 可见光, 重氮化合物, 自由基, 合成

Diazo compounds have rich reactivity and are important synthetic intermediates in organic synthesis. Diazo compounds are commonly used as the precursors of transition metal carbenes, and the relative transition metal catalyzed reactions have achieved many important progresses in the past decades. In sharp contrast, radical reactions with diazo compounds as a key component are still less explored. Owing to the easy generation of diverse radical intermediates under mild conditions, visible-light photoredox catalysis has emerged as a powerful tool for organic synthesis. By the combination of visible light photoredox catalysis and diazo compounds, some novel reactions that different from the classical carbene processes have been developed, which further extend the synthetic applications of these reagents. The progresses of radical reactions of diazo compounds enabled by visible light photoredox catalysis in the past five years are summarized, including: (1) diazo compounds as the nucluophiles, (2) diazo compounds as the equivalents of carbyne precursors, (3) diazo compounds as the radical acceptors, and (4) diazo compounds as the radical precursors. We wish that the detailed discussion on the mechanism of the reactions would help the audiences to understand the features of radical reactions of diazo compounds and the realative visible light chemistry.

Key words: visible light, diazo compound, radical, synthesis