光驱动一步法合成双碳取代双环[1.1.1]戊烷研究进展

doi:10.6023/cjoc202601034

摘要/Abstract

双碳取代双环[1.1.1]戊烷(BCP)因其独特的三维结构和刚性, 在药物化学和材料科学中具有重要应用. 然而, 传统合成方法在制备含特定官能团的BCP衍生物时存在诸多挑战, 如合成步骤繁琐、产率低以及条件苛刻等问题, 严重限制了其大规模制备和深入研究. 因此, 开发绿色高效的合成方法迫在眉睫. 系统综述了近年来一步法合成双碳取代BCP的研究进展, 重点围绕光催化与光诱导两大策略展开, 详细探讨了光催化剂的选择、底物范围及官能团兼容性、反应机理等方面的研究. 在总结现有成果的基础上, 展望了光驱动技术在未来合成BCP衍生物中的应用前景, 并分析了当前面临的挑战和可能的发展方向, 为相关领域的研究者提供了一个全面的参考框架.

关键词: 光催化, 一步法, 双碳取代, 双环[1.1.1]戊烷(BCP), 自由基偶联

Bicyclo[1.1.1]pentane (BCP) derivatives with dual carbon substitutions have gained significant importance in medicinal chemistry and material science due to their distinctive three-dimensional structure and rigidity. However, conventional synthetic methods face considerable challenges in preparing BCP derivatives bearing specific functional groups, including multi-step procedures, low yields, and harsh reaction conditions, which severely hinder their large-scale production and in-depth investigation. Therefore, the development of eco-friendly and efficient synthetic approaches is urgently needed. This review systematically summarizes recent advances in the one-step synthesis of dual carbon-substituted BCPs, with a focus on two major strategies: photocatalysis and photoinduction. It provides a detailed discussion on the selection of photocatalysts, substrate scope and functional group compatibility, as well as underlying reaction mechanisms. Building on current achievements, this review summarizes the future prospects of photocatalysis in synthesizing BCP derivatives, discusses the existing challenges, and proposes potential research directions, thereby offering a comprehensive reference framework for researchers in related fields.

Key words: photocatalysis, one-step, double carbon substitution, bicyclo[1.1.1]pentane (BCP), radical coupling

引用此文

陈安, 王泽艺, 李万梅, 徐骏. 光驱动一步法合成双碳取代双环[1.1.1]戊烷研究进展[J]. 有机化学, 2026, 46(6): 2177-2192.

An Chen, Zeyi Wang, Wanmei Li, Jun Xu. Recent Advances in the Light-Driven One-Step Synthesis of Dual Carbon-Substituted Bicyclo[1.1.1]pentanes[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2177-2192.

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图/表 16

图式1. 分步法合成双碳取代的双环[1.1.1]戊烷

Scheme 1. Stepwise synthesis of bicarbon-substituted bicyclo[1.1.1]pentanes

图式2. 镍/光氧化还原双重催化的[1.1.1]螺桨烷的双官能团化反应

Scheme 2. Dual nickel/photoreduction-catalyzed difunctionalization of [1.1.1]propellane

图式3. 光催化[1.1.1]螺桨烷的杂芳基氟烷基化反应

Scheme 3. Photocatalytic heteroaryl fluoroalkylation of [1.1.1]propellane

图式4. 光催化[1.1.1]螺桨烷的烷基胺化反应

Scheme 4. Photocatalytic alkylamination of [1.1.1]propellane

图式5. 光催化Minisci型多组分合成1-(卤代)烷基-3-杂芳基双环[1.1.1]戊烷反应

Scheme 5. Photocatalytic Minisci-type multicomponent synthesis of 1-(halo)alkyl-3-heteroarylbicyclo[1.1.1]pentanes

图式6. 通过光催化二杂芳基化反应合成1,3-二杂芳基双环[1.1.1]戊烷的反应

Scheme 6. Synthesis of 1,3-diheteroarylbicyclo[1.1.1]pentanes via photocatalytic diheteroarylation reactions

图式7. 金属铜-光协同催化的[1.1.1]螺桨烷的烷基炔基化反应

Scheme 7. Metal-copper-photocatalyzed synergistic alkynylation of [1.1.1]propellane

图式8. 可见光诱导下合成3-杂芳基双环[1.1.1]戊烷-1-乙酸酯的反应

Scheme 8. Visible light-induced synthesis of 3-heteroarylbicyclo[1.1.1]pentane-1-acetates

图式9. 无金属催化剂光氧化还原四组分合成1,3-功能化的三氟甲基双环[1.1.1]戊烷衍生物反应

Scheme 9. Metal-free catalyst photooxidation-reduction four-component synthesis of 1,3-functionalized trifluoromethylbicyclo[1.1.1]pentane derivatives

图式10. 通过能量转移过程合成含有氰基异丙基双环[1.1.1]戊烷基团的杂芳基化合物的反应

Scheme 10. Synthesis of heteroaryl compounds containing cyanoisopropylbicyclo[1.1.1]pentane moieties by an energy transfer process

图式11. 可见光诱导的[1.1.1]螺桨烷直接全氟烷基化/异芳基化反应

Scheme 11. Visible light induced [1.1.1]propellane direct perfluoroalkylation/isoaromatization reaction

图式12. 通过XAT策略光活化多组分合成烷基杂芳基双环[1.1.1]戊烷的反应

Scheme 12. Photo-activated multicomponent synthesis of alkylheteroarylbicyclo[1.1.1]pentanes via the XAT strategy

图式13. 无金属、无氧化剂、无添加剂的多组分合成烷基杂芳基双环[1.1.1]戊烷

Scheme 13. Metal-, oxidant- and additive-free multicomponent synthesis of alkylheteroarylbicyclo[1.1.1]pentanes

图式14. 用于快速合成苯甲酮型生物等排体的光诱导三组分自由基偶联反应

Scheme 14. Light-induced three-component radical coupling reaction for rapid synthesis of benzophenone-type bioisoforms

图式15. 可见光诱导下的[1.1.1]螺桨烷的苄醇官能团化反应

Scheme 15. Visible light-induced benzyl alcohol functionalization of [1.1.1]propellane

图式16. 光诱导的合成含有1,3-二取代双环[1.1.1]戊烷结构的非天然α-氨基酸的反应

Scheme 16. Photo-induced synthesis of unnatural α-amino acids containing 1,3-disubstituted bicyclo[1.1.1]pentane structures

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