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综述与进展

环丙烷骨架的构建及其应用研究进展

郭峻烽, 李春迎*, 胡荣贵, 戎豪杰, 李江伟, 杜咏梅, 秦越, 吕剑*, 孙道安*   

  1. 西安近代化学研究所 氟氮化工新材料全国重点实验室,陕西 西安 710065
  • 基金资助:
    氟氮化工新材料全国重点实验室开放基金 (No. FDKFJJ202502)和X领域国家高层次人才特殊支持计划 (No.X)资助项目

Advances in the Construction Methods of Cyclopropane Skeleton and Their Applications

Guo Jun-feng, Li Chun-ying*, Hu Rong-gui, Rong Hao-jie, Li Jiang-wei, Du Yong-mei, Qing Yue, Lu Jian*, Sun Dao-an*   

  1. State Key Laboratory of Fluorine & Nitrogen Chemical, Xi’an Modern Chemistry Research Institute, Xi’an 710065, Shaanxi, China
  • Contact: *E-mail: sundaoan2008@126.com; chunyingli204@163.com; lujian204@263.net.
  • Supported by:
    Project supported by the the open fund of state key laboratory of fluorine & nitrogen chemical (No. FDKFJJ202502) and national high-level talent special support program in the X field (No. X).

环丙烷骨架因其独特的高张力环结构和良好的脂溶性,在药物化学与燃料化学等多个领域具有重要的理论与应用价值。本文系统综述了近二十年来环丙烷骨架结构的构建策略,涵盖了卡宾/类卡宾与烯烃的环加成反应、叶立德参与的环化反应、金属环丙烷参与的环丙烷化反应、分子内环丙烷化反应,以及新兴的光催化、电催化和酶催化环丙烷化反应等。重点分析了相关反应的机理类型、底物适应性与产物立体选择性。此外,本文还介绍了环丙烷骨架构建策略在药物研发(如抗病毒剂和神经调节剂等活性分子构建)、天然产物全合成及高能燃料分子设计等领域的重要应用进展。最后,展望了环丙烷骨架构建的发展前景,指出开发新型高效催化剂(如纳米负载型与多孔框架型催化剂)、先进光催化技术及绿色的合成新方法是重要发展方向。

关键词: 环丙烷, 卡宾, 环丙烷化反应, 合成策略, 药物, 天然产物, 高能燃料

The cyclopropane skeleton holds significant theoretical and practical value in diverse fields such as medicinal chemistry and fuel chemistry, owing to its highly strained ring structure and favorable lipophilicity. This review systematically summarizes the strategies developed over the past two decades for constructing the cyclopropane framework, including cycloaddition reactions of carbenes and carbenoids with alkenes, ylide-mediated cyclizations, metallocyclopropane-involved cyclopropanations, intramolecular cyclopropanations, as well as emerging photocatalytic, electrocatalytic, and enzymatic cyclopropanation methods. Emphasis is placed on the mechanistic pathways, substrate compatibility, and stereoselectivity of the products. Furthermore, this article highlights recent advances in the application of cyclopropane construction strategies across various domains, such as drug development (e.g., synthesis of antiviral and neuroregulatory agents), total synthesis of natural products, and the design of high-energy-density fuel molecules. Finally, future prospects for the development of cyclopropane synthesis are discussed, pointing to the importance of novel high-efficiency catalysts (e.g., nano-supported and porous framework catalysts), advanced photocatalytic technologies, and greener synthetic methodologies as key research directions.

Key words: Cyclopropane, carbine, Cyclopropanation reaction, Synthetic strategies, Medicines, Natural products, High-energy fuel