四奎烷及类四奎烷全合成研究进展

doi:10.6023/cjoc202408029

摘要/Abstract

多奎烷是指结构上由两个以上环戊烷通过并环方式形成碳骨架的一类天然产物, 其独特的化学结构和潜在的生物活性引起了合成化学家的广泛兴趣. 其中, 具有四个五元全碳环稠合而成的四奎烷以及由三个五元全碳环及一个六元全碳环稠合而成的类四奎烷在结构上最为独特. 本综述按照时间顺序依次总结、介绍四奎烷及类四奎烷的全合成研究进展.

关键词: 天然产物, 多奎烷, 四奎烷, 类四奎烷, 全合成

Polyquinane is a class of natural products composed of multiple fused five-membered carbocycles. Their unique structures and potential biological activities have attracted the interest of the synthetic community. Among them, the structures with four fused five-membered carbocycles (known as tetraquinane), and those with three five-membered carbocycles fused by one six-membered carbocycle that referred to as tetraquinane-type terpenes, are particularly distinctive. This review provides a chronological overview of the total synthesis efforts of tetraquinane and tetraquinane-type terpenes.

Key words: nature products, polyquinane, tetraquinane, tetraquinane-type terpenes, total synthesis

引用此文

杨云博, 丁寒锋. 四奎烷及类四奎烷全合成研究进展[J]. 有机化学, 2025, 45(3): 725-747.

Yunbo Yang, Hanfeng Ding. Advances in the Total Syntheses of Tetraquinane and Tetraquinane-Type Terpenes[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 725-747.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 33

图1. 多奎烷的主要骨架类型及其代表性分子

Figure 1. Main skeletal types of polyquinanes and the representative molecules

图2. 四奎烷与类四奎烷

Figure 2. Teraquinane and teraquinane-type terpenes

图3. 天然产物Crinipellins的结构

Figure 3. Structures of natural products Crinipellins

图式1. Piers课题组对(±)-Crinipellin B的全合成

Scheme 1. Piers’ total synthesis of (±)-Crinipellin B

图式2. Lee课题组对(–)-Crinipellin A的全合成

Scheme 2. Lee’s total synthesis of (–)-Crinipellin A

图式3. 串联[3+2]环加成反应

Scheme 3. [3+2] cycloaddition cascade

图式4. 杨震/龚建贤课题组对(–)-Crinipellins A和B的全合成

Scheme 4. Yang and Gong’s total synthesis of (–)-Crinipellins A and B

图式5. 丁寒锋课题组对(–)-Crinipellins A~F, 以及(–)-Dihydrocrinipellins A和B的全合成(第一部分)

Scheme 5. Ding’s total synthesis of (–)-Crinipellins A~F, and (–)-Dihydrocrinipellins A and B (Part I)

图式6. 丁寒锋课题组对(–)-Crinipellins A~F, 以及(–)-Dihydrocrinipellins A和B的全合成(第二部分)

Scheme 6. Ding’s total synthesis of (–)-Crinipellins A~F, and (–)-Dihydrocrinipellins A and B (Part II)

图式7. 代明骥课题组对(–)-Crinipellins A和B的全合成

Scheme 7. Total synthesis of (–)-Crinipellins A and B by Daiʼs research group

图式8. Cargill重排的两种可能路径

Scheme 8. Two possible ways of the Cargill rearrangement

图4. Bipolarolide D的结构和生源合成途径(a)及相关天然产物(b)

Figure 4. Structure and biosynthetic pathway of Bipolarolide D (a) and relevant natural products (b)

图式9. 陆钊洪课题组对(–)-Bipolarolide D的全合成

Scheme 9. Lu’s total synthesis of (–)-Bipolarolide D

图5. Conidiogenone的结构

Figure 5. Structures of Conidiogenones

图式10. 涂永强课题组对(–)-Conidiogenone B、(–)-Conidiogenone和(–)-Conidiogenol的全合成工作

Scheme 10. Tu’s total synthesis of (–)-Conidiogenone B、(–)-Conidiogenone and (–)-Conidiogenol

图式11. Snyder课题组对(–)-Conidiogenone、(–)-Conidiogenol和(–)-Conidiogenones B~D的全合成

Scheme 11. Snyder’s total synthesis of (–)-Conidiogenone, (–)-Conidiogenol, and (–)-Conidiogenones B~D

图式12. 翟宏斌课题组对(–)-Conidiogenone B、(–)-Conidiogenone和(–)-Conidiogenol的全合成

Scheme 12. Zhai’s total synthesis of (–)-Conidiogenone B, (–)-Conidiogenone and (–)-Conidiogenol

图式13. Lee课题组对(–)-Conidiogenones B~F和(–)-12β-Conidiogenone的全合成(第一部分)

Scheme 13. Lee’s total synthesis of (–)-Conidiogenones B~F, and (–)-12β-Conidiogenone (Part I)

图式14. Lee课题组对(–)-Conidiogenones B~F和(–)-12β-Conidiogenone的全合成(第二部分)

Scheme 14. Lee’s total synthesis of (–)-Conidiogenones B~F, and (–)-12β-Conidiogenone (Part II)

图6. (+)-Waihoensene的结构

Figure 6. Structure of (+)-Waihoensene

图式15. Lee课题组对(±)-Waihoensene的全合成

Scheme 15. Lee’s total synthesis of (±)-Waihoensene

图式16. 杨震/黄俊课题组对(+)-Waihoensene的全合成

Scheme 16. Yang and Huang’s total synthesis of (+)-Waihoensene

图式17. Snyder课题组对(+)-Waihoensene的全合成

Scheme 17. Snyder’s total synthesis of (+)-Waihoensene

图式18. Gaich课题组对(±)-Waihoensene的全合成

Scheme 18. Gaich’s total synthesis of (±)-Waihoensene

图式19. Gaich课题组对(+)-Waihoensene的全合成

Scheme 19. Gaich’s total synthesis of (+)-Waihoensene

图式20. 涂永强课题组对(±)-Waihoensene的全合成

Scheme 20. Tu’s total synthesis of (±)-Waihoensene

图7. (+)-Aberrarone的结构

Figure 7. Structure of (+)-Aberrarone

图式21. Carreira课题组对(+)-Aberrarone的全合成

Scheme 21. Carreira’s total synthesis of (+)-Aberrarone

图式22. Meyer-Schuster重排/Nazarov环化/环丙烷化羟醛缩合串联反应

Scheme 22. Meyer-Schuster rearrangement/Nazarov/cyclopro- panation/aldol cyclization cascade

图式23. 贾彦兴课题组对(+)-Aberrarone的全合成

Scheme 23. Jia’s total synthesis of (+)-Aberrarone

图8. Phomopsenes结构(a)、Phomopsenes及Conidiogenones生源转化关系(b)

Figure 8. Structures of Phomopsenes (a), and biosynthesis relationship with Conidiogenones (b)

图式24. 涂永强/侯四化课题组对(+)-iso-Phomopsene、(–)-Phomopsene和(+)-Methyl Phomopsenonate的全合成

Scheme 24. Tu and Hou’s total synthesis of (+)-iso-Phomopsene, (–)-Phomopsene and (+)-Methyl Phomopsenonate

图式25. Beckmann断裂/重组

Scheme 25. Beckmann fragmentation/recombination

参考文献 37

[1]	(a) Li, H.; Zhang, J.; She, X. Chem.-Eur. J. 2021, 27, 4839.
	(b) Mehta, G.; Srikrishna, A. Chem. Rev. 1997, 97, 671.
[2]	(a) Chen, X.; Yao, W.; Zheng, H.; Wang, H.; Zhou, P.-P.; Zhu, D.-Y.; Wang, S.-H. J. Am. Chem. Soc. 2023, 145, 13549.
	(b) Sun, D.; Chen, R.; Tang, D.; Xia, Q.; Zhao, Y.; Liu, C.-H.; Ding, H. J. Am. Chem. Soc. 2023, 145, 11927.
	(c) Wang, Y.; Yang, C.; Huang, S.-H. Chin. J. Org. Chem. 2024, 44, 1371. (in Chinese)
	(汪洋, 杨晨, 黄莎华, 有机化学, 2024, 44, 1371.)
[3]	Xue, Y.; Hou, S.-H.; Zhang, X.; Zhang, F.-M.; Zhang, X.-M.; Tu, Y.-Q. J. Am. Chem. Soc. 2024, 146, 25445.
[4]	Xu, K.; Mu, S.; Rao, H.; Hu, J.; Ding, H. Angew. Chem., Int. Ed. 2023, 62, e202303668.
[5]	(a) Anke, T.; Heim, J.; Knoch, F.; Mocek, U.; Steffan, B.; Steglich, W. Angew. Chem., Int. Ed. 1985, 24, 709.
	(b) Han, J. W.; Oh, M.; Lee, Y. J.; Choi, J.; Choi, G. J.; Kim, H. Molecules 2018, 23, 2377.
[6]	Piers, E.; Renaud, J. J. Org. Chem. 1993, 58, 11.
[7]	(a) Kang, T.; Song, S. B.; Kim, W.-Y.; Kim, B. G.; Lee, H.-Y. J. Am. Chem. Soc. 2014, 136, 10274.
	(b) Yao, L.; Gui, J. Chin. J. Org. Chem. 2022, 42, 2703. (in Chinese)
	(姚良才, 桂敬汉, 有机化学, 2022, 42, 2703.)
[8]	Hossain, M. L.; Ye, F.; Zhang, Y.; Wang, J. J. Org. Chem. 2013, 78, 1236.
[9]	Huang, Z.; Huang, J.; Qu, Y.; Zhang, W.; Gong, J.; Yang, Z. Angew. Chem., Int. Ed. 2018, 57, 8744.
[10]	(a) Zhao, Y.; Hu, J.; Chen, R.; Xiong, F.; Xie, H.; Ding, H. J. Am. Chem. Soc. 2022, 144, 2495.
	(b) Gao, K.; Hu, J.; Ding, H. Acc. Chem. Res. 2021, 54, 875.
	(c) Liu, Z.; Hu, J.; Ding, H. Org. Lett. 2021, 23, 6745.
	(d) Wang, B.; Liu, Z.; Tong, Z.; Gao, B.; Ding, H. Angew. Chem., Int. Ed. 2021, 60, 14892.
	(e) Hu, J.; Jia, Z.; Xu, K.; Ding, H. Org. Lett. 2020, 22, 1426.
	(f) Gao, J.; Rao, P.; Xu, K.; Wang, S.; Wu, Y.; He, C.; Ding, H. J. Am. Chem. Soc. 2020, 142, 4592.
	(g) He, C.; Bai, Z.; Hu, J.; Wang, B.; Xie, H.; Yu, L.; Ding, H. Chem. Commun. 2017, 53, 8435.
	(h) He, C.; Hu, J.; Wu, Y.; Ding, H. J. Am. Chem. Soc. 2017, 139, 6098.
[11]	Xu, B.; Zhang, Z.; Tantillo, D. J.; Dai, M. J. Am. Chem. Soc. 2024.
[12]	Kozikowski, A. P.; Jung, S. H. J. Org. Chem. 1986, 51, 3400.
[13]	Liu, M.; Sun, W.; Shen, L.; He, Y.; Liu, J.; Wang, J.; Hu, Z.; Zhang, Y. Angew. Chem., Int. Ed. 2019, 58, 12091.
[14]	Li, B.; Tan, C.; Ma, T.; Jia, Y. Angew. Chem., Int. Ed. 2024, 63, e202319306.
[15]	Sun, S.; Wei, Q.; Liu, Y.; Lu, Z. J. Am. Chem. Soc. 2024, 146, 14427.
[16]	Hayashi, Y.; Gotoh, H.; Honma, M.; Sankar, K.; Kumar, I.; Ishikawa, H.; Konno, K.; Yui, H.; Tsuzuki, S.; Uchimaru, T. J. Am. Chem. Soc. 2011, 133, 20175.
[17]	Roncal, T.; Cordobés, S.; Sterner, O.; Ugalde, U. Eukaryotic Cell 2002, 1, 823.
[18]	Hou, S.-H.; Tu, Y.-Q.; Wang, S.-H.; Xi, C.-C.; Zhang, F.-M.; Wang, S.-H.; Li, Y.-T.; Liu, L. Angew. Chem., Int. Ed. 2016, 55, 4456.
[19]	Hu, P.; Chi, H. M.; DeBacker, K. C.; Gong, X.; Keim, J. H.; Hsu, I. T.; Snyder, S. A. Nature 2019, 569, 703.
[20]	Xu, B.; Xun, W.; Su, S.; Zhai, H. Angew. Chem., Int. Ed. 2020, 59, 16475.
[21]	Kim, J.; Lee, S.; Han, S.; Lee, H.-Y. Chem 2023, 9, 1270.
[22]	Clarke, D. B.; Hinkley, S. F. R.; Weavers, R. T. Tetrahedron Lett. 1997, 38, 4297.
[23]	Xin, Z.; Wang, H.; He, H.; Gao, S. Tetrahedron Lett. 2021, 71.
[24]	Lee, H.; Kang, T.; Lee, H.-Y. Angew. Chem.,Int. Ed. 2017, 56, 8254.
[25]	Qu, Y.; Wang, Z.; Zhang, Z.; Zhang, W.; Huang, J.; Yang, Z. J. Am. Chem. Soc. 2020, 142, 6511.
[26]	(a) Brown, M. K.; May, T. L.; Baxter, C. A.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2007, 46, 1097.
	(b) Bleschke, C.; Tissot, M.; Mueller, D.; Alexakis, A. Org. Lett. 2013, 15, 2152.
[27]	Peng, C.; Arya, P.; Zhou, Z.; Snyder, S. A. Angew. Chem., Int. Ed. 2020, 59, 13521.
[28]	May, T. L.; Brown, M. K.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2008, 47, 7358.
[29]	Rosenbaum, L.-C.; Haefner, M.; Gaich, T. Angew. Chem., Int. Ed. 2021, 60, 2939.
[30]	Wang, Y.-P.; Fang, K.; Tu, Y.-Q.; Yin, J.-J.; Zhao, Q.; Ke, T. Nat. Commun. 2022, 13, 2335.
[31]	Rodriguez, I. I.; Rodriguez, A. D.; Zhao, H. J. Org. Chem. 2009, 74, 7581.
[32]	Amberg, W. M.; Carreira, E. M. J. Am. Chem. Soc. 2022.
[33]	Lemiere, G.; Gandon, V.; Cariou, K.; Fukuyama, T.; Dhimane, A.-L.; Fensterbank, L.; Malacria, M. Org. Lett. 2007, 9, 2207.
[34]	Wang, Y.; Su, Y. J.; Jia, Y. X. J. Am. Chem. Soc. 2023, 145, 9459.
[35]	Toyomasu, T.; Kaneko, A.; Tokiwano, T.; Kanno, Y.; Kanno, Y.; Niida, R.; Miura, S.; Nishioka, T.; Ikeda, C.; Mitsuhashi, W.; Dairi, T.; Kawano, O.; Oikawa, H.; Kato, N.; Sassa, T. J. Org. Chem. 2009, 74, 1541.
[36]	Yin, J.-J.; Wang, Y.-P.; Xue, J.; Zhou, F.-F.; Shan, X.-Q.; Zhu, R.; Fang, K.; Shi, L.; Zhang, S.-Y.; Hou, S.-H.; Xia, W.-J.; Tu, Y. Q. J. Am. Chem. Soc. 2023, 145, 21170.
[37]	Fang, K.; Dou, B.-H.; Zhang, F.-M.; Wang, Y.-P.; Shan, Z.-R.; Wang, X.-Y.; Hou, S.-H.; Tu, Y.; Ding, T.-M. Angew. Chem., Int. Ed. 2024, e202412337.