有机化学    

综述与进展

配体辅助电荷转移驱动的光促铁催化

吉伟文a, 叶宁b,*, 金健a,*   

  1. a中国科学院上海有机化学研究所 生命过程小分子调控全国重点实验室 上海 200032;
    b宁康瑞珠生物制药(珠海)有限公司 珠海 519070
  • 收稿日期:2026-01-24 修回日期:2026-03-14
  • 基金资助:
    国家重点研发计划(No. 2023YFA0914500)资助项目.

Ligand-Facilitated LMCT-Driven Photoinduced Iron Catalysis

Ji Weiwena, Ye Ningb,*, Jin Jiana,*   

  1. aState Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032;
    bRezubio Pharmaceuticals Co. Ltd., Zhuhai, 519070
  • Received:2026-01-24 Revised:2026-03-14
  • Contact: *E-mail: jjin@sioc.ac.cn; ning.ye@rezubio.com
  • Supported by:
    National Key Research and Development Program of China (No. 2023YFA0914500).

铁在地壳中储量丰富且生物兼容性好,发展铁基光催化符合绿色可持续化学的需求。近年来,基于配体-金属电荷转移(LMCT)机制的光促铁催化反应取得了显著进展。该策略利用光激发铁-底物(或试剂)配合物,引发分子内电子转移产生高活性的自由基物种,从而在温和条件下实现丰富多样的有机转化。本文系统综述了配体辅助的LMCT驱动的光促铁催化反应的最新研究进展。根据参与LMCT过程的底物(或试剂)类型,文章分章节详细讨论了烷基羧酸、草氨酸、含氟烷基羧酸、芳基羧酸、醇、水、叠氮及氯化物等体系的反应设计。重点阐述了配体(如吡啶甲酸、多吡啶胺等)在调节铁中心氧化还原性质、延长激发态寿命及提升可见光吸收效率方面的关键作用,并总结了相关反应机理及合成应用。最后,对该领域面临的挑战及未来的发展方向进行了展望。

关键词: 配体辅助, 电荷转移驱动, 光促, 铁催化, 自由基反应

Iron is the second most abundant metal in the earth's crust and possesses excellent biocompatibility, making the development of iron photocatalysis highly desirable for green and sustainable chemistry. In recent years, photoinduced iron catalysis driven by ligand-to-metal charge transfer (LMCT) has witnessed significant progress. This strategy involves the photoexcitation of iron-substrate (or reagent) complexes to induce intramolecular electron transfer, generating highly reactive radical species that trigger diverse organic transformations under mild conditions. This review systematically summarizes recent advances in ligand-facilitated LMCT-driven photoinduced iron catalysis. The discussions are categorized based on the types of substrates (or reagents) involved in the LMCT process, covering systems such as alkyl carboxylic acids, oxamic acids, fluorinated alkyl carboxylic acids, aryl carboxylic acids, alcohols, water, azides, and chlorides. Special emphasis is placed on the critical role of ligands (e.g., picolinic acids, polypyridyl amines) in tuning the redox properties of the iron center, prolonging excited-state lifetimes, and enhancing visible light absorption. The reaction mechanisms and synthetic applications are also discussed. Finally, the challenges and future prospects of this emerging field are highlighted.

Key words: ligand-facilitated, LMCT-driven, photoinduced, iron catalysis, radical reaction