酰基自由基化学在天然产物全合成中的应用

doi:10.6023/cjoc202409033

摘要/Abstract

酰基自由基具有独特的结构特征和高反应活性, 受到有机合成化学家的广泛关注. 近年来, 随着其来源和引发方式的不断创新, 酰基自由基在各种化学转化中的应用日益广泛; 特别是在天然产物合成后期的关键步骤中, 酰基自由基因的较小位阻以及不易发生金属介导的β-消除反应等优势, 成为兼容多种官能团行之有效的策略之一. 此文综述了近年来通过酰基自由基化学作为关键步骤在复杂天然产物合成中的应用.

关键词: 酰基自由基, 天然产物, 全合成, 自由基环化

Acyl radicals have received extensive attention from organic synthetic chemists due to their unique structural features and high reactivity. In recent years, with the continuous innovation of their acyl sources and initiation modes, acyl radicals have been widely used in various chemical transformations. Especially in the critical step of the late stage of natural product synthesis, acyl radicals have become one of the effective and important strategies compatible with a wide range of functional groups due to the advantages of their smaller site resistance and less susceptibility to metal-mediated β-elimination reactions. Application of acyl radicals as a key step in the synthesis of natural products is summarized.

Key words: acyl radicals, natural products, total synthesis, radical cyclization

引用此文

谢应, 付绍敏, 刘波. 酰基自由基化学在天然产物全合成中的应用[J]. 有机化学, 2025, 45(3): 852-861.

Ying Xie, Shaomin Fu, Bo Liu. Application of Acyl Radical in Total Synthesis of Natural Products[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 852-861.

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图/表 22

图式1. 酰基自由基在天然产物合成中的应用

Scheme 1. Application of acyl radicals in the synthesis of natural products

图式2. 天然产物coniine的全合成

Scheme 2. Total synthesis of coniine

图式3. 天然产物hinokinin和dihydrocapsaicin的全合成

Scheme 3. Total synthesis of hinokinin and dihydrocapsaicin

图式4. 天然产物roseophilin的全合成

Scheme 4. Total synthesis of roseophilin

图式5. 天然产物himbacine核心骨架的构建

Scheme 5. Construction of the himbacine core skeleto

图式6. 天然产物guatambuine的全合成

Scheme 6. Total synthesis of guatambuine

图式7. 天然产物calothrixin B的全合成

Scheme 7. Total synthesis of calothrixin B

图式8. 酰基自由基环化构建uleine的核心骨架

Scheme 8. Acyl radical cyclization constructs the core backbone of uleine

图式9. 酰基自由基环化构建actinophyllic acid的核心骨架

Scheme 9. Acyl radical cyclization constructs the core skeleton of actinophyllic acid

图式10. 天然产物acanthodoral的全合成

Scheme 10. Total synthesis of acanthodoral

图式11. 酰基自由基构建聚醚类天然产物片段

Scheme 11. Acyl free construction of polyether natural product fragments

图式12. 天然产物strophasterols A和B的全合成

Scheme 12. Total synthesis of strophasterols A and B

图式13. 天然产物No. 2106A的全合成

Scheme 13. Total synthesis of No. 2106A

图式14. 天然产物pinnigorgiols B和E的全合成

Scheme 14. Total synthesis of pinnigorgiols B and E

图式15. 天然产物clionastatins A和B的全合成

Scheme 15. Total synthesis of clionastatins A and B

图式16. 天然产物allokainic的全合成

Scheme 16. Total synthesis of allokainic

图式17. 天然产物(±)-isopalhinine A、(±)-palhinines A和D的仿生合成

Scheme 17. Biomimetic syntheses of (±)-isopalhinine A, (±)-palhinines A and D

图式18. 天然产物cotylenin A的汇聚式合成

Scheme 18. Convergent synthesis of cotylenin A

图式19. 天然产物brevione C的全合成

Scheme 19. Total synthesis of brevione C

图式20. 天然产物flueggeacosine B的全合成

Scheme 20. Total synthesis of flueggeacosine B

图式21. 酰基自由基环化/重排反应构建双环[2.2.2]辛酮

Scheme 21. Construction of bicyclo[2.2.2]octanones by acyl radical cyclization/rearrangement reactions

图式22. 光催化烷基醛和炔的[3+2]环加成反应

Scheme 22. Photocatalytic [3+2] cycloaddition of alkyl aldehydes and alkynes

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