有机大共轭分子C—H亲核取代反应的研究进展

摘要/Abstract

有机大共轭分子凭借其独特的扩展π电子体系, 在材料化学、药物化学及化学生物学等领域展现出重要且广泛的应用价值. 对大共轭分子进行官能团化以调控其性质, 已成为化学研究领域备受关注的重要议题之一. 目前, 大共轭分子的后修饰方法研究相对较少, 主要依赖于芳香亲电取代和过渡金属催化的偶联反应等常规策略. 系统综述了基于大共轭分子的独特C—H亲核取代反应的研究进展, 涵盖了经典体系如卟啉、硼二吡咯亚甲基(BODIPYs)、薁烯以及一些其他大共轭分子. 研究表明, 通过优化反应条件, 选用合适的亲核试剂、导向基团与添加剂, 可以实现对特定C—H键的高效亲核取代官能团化, 从而构建具有特定结构与功能的化合物. 不仅将深化对亲核取代反应机制的理解, 还为构建具有独特功能的π共轭体系开辟了新途径.

关键词: 大共轭分子, π-电子体系, 亲核取代, C—H官能团化

Organic largely conjugated molecules, characterized by their delocalized π-electron systems, exhibit significant and broad application potential in fields such as materials chemistry, medicinal chemistry, and chemical biology. Functionalizing these conjugated systems to modulate their properties has become a major focus in chemical research. However, current methods for late-stage modification of extended conjugated molecules remain limited, primarily relying on conventional strategies such as electrophilic aromatic substitution and transition-metal-catalyzed coupling reactions. The recent advances in unique C—H nucleophilic substitution reactions on extended conjugated molecules are systematically summarized, covering classical systems such as porphyrins, boron-dipyrromethenes (BODIPYs), azulene, and some other large conjugated molecules. Studies have demonstrated that by optimizing reaction conditions, selecting suitable nucleophiles, directing groups and additive, efficient functionalization of specific C—H bonds can be achieved, enabling the construction of compounds with tailored structures and functions. This review not only deepens the understanding of nucleophilic substitution mechanisms but also opens new avenues for designing π-conjugated systems with unique functionalities.

Key words: largely conjugated system, π-electron system, nucleophilic substitution, C—H functionalization

引用此文

白燕茹, 周来运, 刘广华, 王青. 有机大共轭分子C—H亲核取代反应的研究进展[J]. 有机化学, 2026, 46(5): 1883-1896.

Yanru Bai, Laiyun Zhou, Guanghua Liu, Qing Wang. Research Progress on C—H Nucleophilic Substitution Reactions of Organic Largely Conjugated Molecules[J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 1883-1896.

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图/表 19

图式1. 卟啉类化合物的结构及其亲核反应机理示例

Scheme 1. Examples of the structures of porphyrin derivatives and their nucleophilic reaction mechanism

图式2. sp3杂化的碳亲核试剂对卟啉meso-位点的亲核取代反应

Scheme 2. Nucleophilic substitution reactions of sp3 hybridized carbon nucleophiles to the meso-sites of porphyrins

图式3. sp2杂化碳亲核试剂对卟啉meso-位点的亲核取代反应

Scheme 3. Nucleophilic substitution reactions of sp2-hybridized carbon nucleophiles to the meso-sites of porphyrins

图式4. sp杂化碳亲核试剂对卟啉meso-位点的亲核取代反应

Scheme 4. Nucleophilic substitution reactions of sp-hybridized carbon nucleophiles on the meso-sites of porphyrins Ar=3,5-di-tert-butylphenol, a 12 h, the reaction time for all unmarked reactions is 3 h, CM=mixture

图式5. 卟啉β-位点的C—H亲核取代反应

Scheme 5. C—H nucleophilic substitution reactions at the β-sites of porphyrin

图式6. N-杂卟啉在L-脯氨酸存在下的反应及可能机理

Scheme 6. Reactions and putative mechanisms of N-confused porphyrins in the presence of L-proline

图式7. Norcorrole型卟啉β-位点的亲核取代反应

Scheme 7. Nucleophilic substitution reactions at the β-sites of Norcorrole-type porphyrins

图式8. Corrole型卟啉β-位点的亲核取代反应

Scheme 8. Nucleophilic substitution reactions at the β-sites of Corrole-type porphyrins

图式9. BODIPYs类化合物亲核取代反应机理图

Scheme 9. Diagram of the nucleophilic substitution reaction mechanism of BODIPYs compounds

图式10. BODIPYs类化合物α-位点的C—H亲核取代反应

Scheme 10. C—H nucleophilic substitution reactions at the α-sites of BODIPYs derivatives

图式11. BODIPYs类化合物在Pb(OAc)4促进下的C—H亲核取代反应

Scheme 11. C—H nucleophilic substitution reactions of BODIPYs derivatives promoted by Pb(OAc)4

图1. 萘和薁烯HOMO的对称轴以及薁烯的反应位点

Figure 1. Symmetry axis of the HOMO of naphthalene and azulene, as well as the reaction site of azulene

图式12. 薁烯C4和C6位点的C—H亲核取代反应

Scheme 12. C—H nucleophilic substitution reactions at the C4 and C6 sites of azulene

图式13. 薁烯衍生物C-6位点的C—H亲核取代反应

Scheme 13. C—H nucleophilic substitution reaction at the C-6 site of azulene derivatives

图式14. C—H亲核取代反应的EPE转移步骤机理图及氮杂稠环中的C—H亲核取代反应

Scheme 14. Mechanistic diagram of the electrophile-promoted electrophilic (EPE) transfer step in C—H nucleophilic substitution and C—H nucleophilic substitution in nitrogen-containing fused heterocycles

图式15. 并苯类化合物的C—H亲核取代反应

Scheme 15. Nucleophilic substitution of C—H bonds in acenes

图式16. ICl参与的大共轭分子的C—H亲核取代反应

Scheme 16. Nucleophilic substitution of C—H bonds in large conjugated molecules involving ICl

图式17. 1-R-乙炔基-9,10-蒽醌的C—H亲核取代反应

Scheme 17. Nucleophilic substitution reaction of 1-R-ethynyl- 9,10-anthraquinone

图式18. triangulenedione和anthanthrone的亲核取代反应

Scheme 18. Nucleophilic substitution reaction of triangulenedione and anthanthrone

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