多卤代海洋来源天然产物全合成

doi:10.6023/cjoc202408037

摘要/Abstract

卤素掺入是海洋生物用于修饰其多用途代谢物的一种独特策略, 通常会导致生物活性以及体内代谢或降解历程的改变. 同时, 卤素的引入也会增加海洋天然产物结构的复杂性及其鉴定难度. 近年来多卤取代的海洋来源天然产物独特的化学结构与多样性的生物学功能引起了有机合成化学家的广泛兴趣. 此综述将从多卤吲哚生物碱(Caulamidines, Perophoramidine, Hinckdentine A, Spiroindimicins, Dictazole B, Securiflustra securifrons, Nortopsentin D)、其它多卤生物碱(Psammaplysins, Massadine, Axinellamine, Discorhabdins)和典型多卤甾体天然产物(Clionastatins)三个方面总结近年来多卤取代的海洋来源天然产物全合成的研究进展.

关键词: 海洋多卤天然产物, 天然产物, 全合成

The incorporation of halogens is a unique strategy employed by marine organisms to modify their multifunctional metabolites, often leading to changes in biological activity and the metabolic or degradation processes in vivo. At the same time, the introduction of halogens increases the structural complexity of marine natural products, making their identification more challenging. In recent years, the unique chemical structures and diverse biological functions of polyhalogenated marine-derived natural products have garnered significant interest from organic synthetic chemists. Recent advances in the total synthesis of polyhalogenated marine-derived natural products, focusing on polyhalogenated indole alkaloids (Caulamidines, Perophoramidine, Hinckdentine A, Spiroindimicins, Dictazole B, Securiflustra securifrons, Nortopsentin D), other polyhalogenated alkaloids (Psammaplysins, Massadine, Axinellamine, Discorhabdins), and representative polyhalogenated steroidal natural products (Clionastatins) are summarized.

Key words: marine polyhalogenated natural product, natural product, total synthesis

引用此文

杨庆星, 刘璇, 马硕, 李欣欣, 马东旭, 徐涛. 多卤代海洋来源天然产物全合成[J]. 有机化学, 2025, 45(3): 764-803.

Qingxing Yang, Xuan Liu, Shuo Ma, Xinxin Li, Dongxu Ma, Tao Xu. Total Syntheses of Marine-Derived Polyhalogenated Natural Products[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 764-803.

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图/表 44

图1. Caulamidines生物碱家族成员

Figure 1. Family members of Caulamidines alkaloids

图式1. Maimone课题组对(–)-Caulamidine A的全合成

Scheme 1. The first total synthesis of (–)-Caulamidine A by Maimone’s group

图式2. 徐涛课题组对(–)-Caulamidine D和(–)-Isocaulamidine D的对映选择性全合成.

Scheme 2. The first enantioselective total synthesis of (–)-Caulamidine D and (–)-Isocaulamidine D by Xu’s group

图式3. Funk课题组对Perophoramidine的全合成

Scheme 3. Total synthesis of Perophoramidine by Funk’s group

图式4. 秦勇课题组对(+)-Perophoramidine的不对称全合成

Scheme 4. Total enantioselective synthesis of (+)-Perophoramidine by Qin’s group

图式5. 王锐课题组对(+)-Perophoramidine的不对称全合成

Scheme 5. Total enantioselective synthesis of (+)-Perophoramidine by Wang’s group

图式6. Trost课题组对(–)-Perophoramidine的不对称全合成

Scheme 6. Total enantioselective synthesis of (–)-Perophoramidine by Trost’s group

图式7. Stoltz课题组对(+)-Perophoramidine的形式全合成

Scheme 7. Formal synthesis of (+)-Perophoramidine by Stoltz’s group

图式8. Kawasaki课题组对(±)-Hinckdentine A的全合成.

Scheme 8. Total synthesis of (±)-Hinckdentine A by Kawasaki’s group

图式9. Fukuyama和Kitamura课题组对(+)-Hinckdentine A的不对称全合成.

Scheme 9. Asymmetric total synthesis of (+)-Hinckdentine A by Fukuyama and Kitamura’s group

图式10. 祝介平课题组对(+)-Hinckdentine A的不对称全合成

Scheme 10. Asymmetric total synthesis of (+)-Hinckdentine A by Zhu’s group

图式11. 徐海超课题组对(±)-Hinckdentine A的全合成

Scheme 11. Total synthesis of (±)-Hinckdentine A by Xu’s group

图式12. Cheon课题组对(±)-Hinckdentine A的全合成

Scheme 12. Total synthesis of (±)-Hinckdentine A by Cheon’s group

图式13. 洪然课题组对(+)-Hinckdentine A的不对称全合成

Scheme 13. Asymmetric total synthesis of (+)-Hinckdentine A by Hong’s group

图式14. Rawal课题组对(+)-Hinckdentine A的不对称全合成

Scheme 14. Asymmetric total synthesis of (+)-Hinckdentine A by Rawal’s group

图2. Spiroindimicins生物碱

Figure 2. Spiroindimicin alkaloids

图式15. Sperry课题组对Spiroindimicin B/C的全合成

Scheme 15. Total synthesis of Spiroindimicin B/C by Sperry’s group

图式16. Smith课题组对Spiroindimicin A的全合成

Scheme 16. Total synthesis of Spiroindimicin A by Smith’s group

图式17. 徐正仁课题组对Spiroindimicin A的全合成

Scheme 17. Total synthesis of Spiroindimicin A by Xu’s group

图式18. Smith课题组对5/5-Spirocyclic spiroindimicins模块化全合成

Scheme 18. Modular total synthesis of 5/5-Spirocyclic spiroindimicins by Smith’s group

图3. Aplysinopsins类型生物碱的几种代表化合物

Figure 3. Several representative compounds of Aplysinopsins type alkaloids

图式19. (±)-Dictazole B合成前体的制备

Scheme 19. Preparation of precursor for (±)-Dictazole B synthesis

图式20. 模拟日光照射下固态条件的二聚化反应

Scheme 20. Solid-state dimerization under irradiation with artificial sunligh

图式21. DNA模板促进的[2+2]环加成

Scheme 21. Rationalization of the DNA-templated [2+2] cycloaddition

图4. 多卤代生物碱Securiflustra securifrons和Chartelline C

Figure 4. Polyhalogenated alkaloids Securiflustra securifrons and Chartelline C

图式22. Baran课题组对(±)-Chartelline C的合成

Scheme 22. Synthesis of (±)-Charteline C by Baran’s group

图式23. Herzon课题组对(±)-Securine A和(±)-Securamine A的合成

Scheme 23. Synthesis of (±)-Securine A and (±)-Securamine A by Herzon’s group

图式24. Herzon课题组对Securiflustra securifrons家族其他生物碱的合成

Scheme 24. Synthesis of other Securiflustra securifrons’ alkaloids by Herzon’s group

图5. Nortopsentin类型生物碱及其合成类似物

Figure 5. Nortopsentin type alkaloids and their synthetic analogues

图式25. Tepe课题组对Nortopsentin D的合成

Scheme 25. Synthesis of Nortopsentin D by Tepe’s group

图式26. Magauer课题组对(±)-Psammaplysin A的合成

Scheme 26. Synthesis of (±)-Psammaplysin A by Magauer’s group

图式27. Smith课题组对Psammaplysins A, M, O, Q和Ceratinamide A的全合成

Scheme 27. Synthesis of Psammaplysins A, M, O, Q and Ceratinamide A by Smith’s group

图式28. 杨震课题组对7?Deoxypsammaplysins K, O和7?Deoxyceratinamide A的合成

Scheme 28. 7?Deoxypsammaplysins K, O and 7?Deoxyceratinamide A by Yang’s group

图式29. Baran对Massadine的合成

Scheme 29. Total synthesis of Massadine by Baran

图式30. Chuo和Baran对于Sceptrin的全合成工作

Scheme 30. Total synthesis of Sceptrin by Chuo and Baran

图式31. Baran对于Nakamuric acid的全合成

Scheme 31. Total synthesis of Nakamuric acid by Baran

图式32. Baran对于Axinellamines的全合成

Scheme 32. Total synthesis of Axinellamines by Baran

图式33. Chuo对于Axinellamines的全合成工作

Scheme 33. Total synthesis of Axinellamines by Chuo

图6. 代表性的Discorhabdins生物碱家族的分子

Figure 6. Completely synthesized molecules of the Discorhabdins alkaloid family

图式34. Yamamura研究组关于Discorhabdin C的合成

Scheme 34. Yamamura’s group on the synthesis of Discorhabdin C

图式35. Kita研究组关于Discorhabdin C的合成

Scheme 35. Synthesis of Discorhabdin C by Kita’s group

图式36. Heathcock研究组关于Discorhabdins C和E的合成

Scheme 36. Synthesis of Discorhabdins C and E by Heathcock’s group

图式37. 桂敬汉课题组对于Clionastatins的全合成工作

Scheme 37. Total synthesis of Clionastatins by Gui’s group

图式38. 张延东课题组对于Clionastatins的全合成工作

Scheme 38. Total synthesis of Clionastatins by Zhang’s group

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