有机化学    

综述与进展

过渡金属催化1,3-二烯的不对称环化反应研究进展

沈国礼*,a,b,c, 何玥a, 景士文a, 安子博a,b,c, 徐丹丹*,a   

  1. a天水师范大学化学工程与技术学院 天水 741001;
    b甘肃省先进光电功能材料重点实验室 天水 741001;
    c甘肃省高校新型分子材料设计与功能省级重点实验室 天水 741001
  • 收稿日期:2025-10-10 修回日期:2025-11-16
  • 基金资助:
    甘肃省青年科技基金(No. 25JRRE011),陇原青年创新创业人才(No. 2025QNTD08),天水师范大学(No. KYQ2023-12、No. GJB2024-01)资助项目.

Research Progress on Transition Metal-Catalyzed Asymmetric Cyclization Reactions of 1,3-Dienes

Shen, Guoli*,a,b,c, He, Yuea, Jing, Shiwena, An, Ziboa,b,c, Xu, Dandan*,a   

  1. aCollege of Chemical Engineering and technology, Tianshui Normal University, Tianshui 741001;
    bKey Laboratory of Advanced Optoelectronic Functional Materials of Gansu Province, Tianshui 741001;
    cKey Laboratory for New Molecule Materials Design and Function of Gansu Universities, Tianshui 741001
  • Received:2025-10-10 Revised:2025-11-16
  • Contact: *E-mail: shenguoli0208@163.com, 18837053307@163.com
  • Supported by:
    Youth Science and Technology Foundation of Gansu (No. 25JRRE011), the Youth Innovation and Entrepreneurship Talent Project of Gansu Province (No. 2025QNTD08), the Tianshui Normal University (No. KYQ2023-12、No. GJB2024-01).

过渡金属催化的1,3-二烯不对称环化反应是构建手性环状分子的重要策略, 在天然产物、药物分子及功能材料的合成中具有广泛应用. 本文系统介绍了近年来该领域的研究进展, 重点围绕1,2-位和1,4-位环化两种模式, 详细讨论了Heck反应、C-H键活化、Wacker-type氧化以及π-Lewis碱催化等多种策略介导的串联环化反应. 这些方法能够高效、高对映选择性地构建从五元到八元环的多种环系, 并展现出良好的官能团兼容性和底物多样性. 尽管该领域已取得显著成果, 但仍面临机理不明确、底物普适性有限、手性控制不足等挑战. 未来需通过机理深入研究、新型廉价金属催化剂开发以及底物范围拓展, 进一步推动该类反应的发展与应用.

关键词: 过渡金属, 1,3-二烯, 不对称环化

Transition metal-catalyzed asymmetric cyclization reactions of 1,3-dienes represent a powerful strategy for the construction of chiral cyclic compounds, with broad applications in the synthesis of natural products, pharmaceuticals, and functional materials. This article systematrically reviews recent advances in this field, focusing on two major cyclization modes 1,2-and 1,4-cyclication, and provides a detailed discussions, including Heck reactions, C-H bond activation, Wacker-type oxidations, and π-Lewis base catalysis. These methods enable efficient and highly enantioselective construction of various ring systems ranging from five-to eight-membered cycles, demonstrating good functional group compatibility and substrate diversity. Despite significant progress, challenges remain, such as unclear mechanisms, limited substrate scope, and insufficient stereocontrol . Future developments should focus on in-depht mechanistic elucidation, the design of economical metal catalysts, and the expansion of substrate generality to enhance the utility of these transformations.

Key words: Transition metal, 1,3-Dienes, Asymmetric cyclization