有机化学 ›› 2026, Vol. 46 ›› Issue (4): 1330-1359.DOI: 10.6023/cjoc202512029 上一篇    下一篇

综述与进展

过渡金属催化自由基介导1,3-二烯的选择性双官能团化研究进展

刘水林a, 陈镤a,*(), 贺晶a, 刘宁a,*(), 黄华文b,c,*()   

  1. a 湖南工学院化学与环境工程学院 湖南衡阳 421200
    b 湘潭大学化学学院 湖南湘潭 411100
    c 河南师范大学化学化工学院 河南新乡 453007
  • 收稿日期:2025-12-29 修回日期:2026-01-26 发布日期:2026-03-20
  • 通讯作者: 陈镤, 刘宁, 黄华文
  • 基金资助:
    国家自然科学基金(22071211); 湖南省教育厅重点项目(22A0631); 湖南省教育厅重点项目(22A0628); 湖南省自然科学基金区域联合项目(2025JJ70140); 及湖南省大学生创新创业训练计划(S202511528219S)

Recent Advances in Transition Metal-Catalyzed Radical-Mediated Selective Difunctionalization of 1,3-Dienes

Shuilin Liua, Pu Chena,*(), Jing Hea, Ning Liua,*(), Huawen Huangb,c,*()   

  1. a College of Chemistry and Environmental Engineering, Hunan Institute of Technology, Hengyang, Hunan 421200
    b College of Chemistry, Xiangtan University, Xiangtan, Hunan 411100
    c School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007
  • Received:2025-12-29 Revised:2026-01-26 Published:2026-03-20
  • Contact: Pu Chen, Ning Liu, Huawen Huang
  • Supported by:
    National Natural Science Foundation of China(22071211); Key Projects of Hunan Provincial Department of Education(22A0631); Key Projects of Hunan Provincial Department of Education(22A0628); Regional Joint Project of Hunan Provincial Natural Science Foundation(2025JJ70140); Hunan Provincial College Students’ Innovative Entrepreneurship Training Program Project(S202511528219S)

近年来, 自由基化学的蓬勃发展与过渡金属催化策略的深度融合, 为有机合成提供了高效构筑复杂分子的新范式. 与传统离子型反应相比, 自由基反应具有条件温和、官能团兼容性好以及能够快速构建复杂分子等独特优势, 因而受到合成化学家的持续关注. 1,3-二烯作为一类来源广泛、结构丰富的基础化工原料, 广泛存在于天然产物及功能分子骨架中, 其选择性双官能团化一直是有机合成的重要挑战与研究热点. 借助自由基途径, 特别是结合过渡金属催化的协同作用, 不仅能够突破传统极性反应的局限, 拓展新颖的化学空间, 还可实现一锅法高效引入两个不同官能团, 精准构建高附加值的烯丙基类化合物. 系统总结了近三年来的研究进展, 重点聚焦于不同过渡金属催化、自由基前体开发、反应机制演变以及代表性催化体系构建, 并结合典型实例深入探讨其合成应用与前景, 旨在为该领域的持续创新提供理论参考与方法启示.

关键词: 过渡金属催化, 自由基, 1,3-二烯, 双官能团化, 选择性

In recent years, the rapid advancement of radical chemistry and its deep integration with transition metal catalysis have established a powerful new paradigm for the efficient construction of complex molecules in organic synthesis. Compared with traditional ionic reactions, radical reactions offer unique advantages such as mild reaction conditions, good functional group compatibility, and the ability to rapidly build molecular complexity, which have garnered sustained attention from synthetic chemists. 1,3-Dienes, as a class of readily available and structurally diverse building blocks, are widely embedded in natural products and functional molecules, and their selective difunctionalization remains a significant challenge and an active area of research. Radical-based strategies, particularly when synergized with transition metal catalysis, not only overcome the limitations of conventional polar reactivity, but also unlock novel chemical space, enabling the one-pot, simultaneous incorporation of two distinct functional groups to afford high-value allylic compounds with precision. A systematic overview of key advances over the past three years is provided. Emphasis is placed on the development of diverse transition metal catalysts, innovative radical precursors, evolving mechanistic understanding, and representative catalytic systems. Through illustrative examples, their synthetic applications and future potential are further discussed, aiming to offer both conceptual insights and practical guidance to inspire continued innovation in this dynamic field.

Key words: transition metal catalysis, radical, 1,3-diene, difunctionalization, selectivity