Wagner-Meerwein重排反应在天然产物全合成中的应用

doi:10.6023/cjoc202408010

有机化学 ›› 2025, Vol. 45 ›› Issue (3): 896-912.DOI: 10.6023/cjoc202408010 上一篇下一篇

综述与进展

Wagner-Meerwein重排反应在天然产物全合成中的应用

陈杰^a, 李俊^a, 龙先文^a, 申海香^b^,^*(), 邓军^a^,^*()

a 南开大学化学学院元素有机化学国家重点实验室天津 300071
b 武威职业学院现代农业学院甘肃武威 733000

收稿日期:2024-08-07 修回日期:2024-09-10 发布日期:2024-10-29
通讯作者: 申海香, 邓军
基金资助:
国家自然科学基金(22188101); 国家自然科学基金(22222105); 国家自然科学基金(22301146); 国家自然科学基金(22371142); 南开大学有机新物质创造前沿科学中心(63181206); 中央高校基本科研业务费(23JCYBJC01410); 中国博士后基金(332608)

Recent Advances of Wagner-Meerwein Rearrangement in Natural Product Synthesis

Jie Chen^a, Jun Li^a, Xianwen Long^a, Haixiang Shen^b(), Jun Deng^a()

a State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071
b College of Advanced Agricultural Sciences, Wuwei Occupational College, Wuwei, Gansu 733000

Received:2024-08-07 Revised:2024-09-10 Published:2024-10-29
Contact: Haixiang Shen, Jun Deng
Supported by:
National Natural Science Foundation of China(22188101); National Natural Science Foundation of China(22222105); National Natural Science Foundation of China(22301146); National Natural Science Foundation of China(22371142); Frontiers Science Center for New Organic Matter, Nankai University(63181206); Fundamental Research Funds for the Central Universities(23JCYBJC01410); China Postdoctoral Science Foundation(332608)

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摘要/Abstract

Wagner-Meerwein重排反应因其在分子内高效构建季碳手性中心和实现碳骨架重组的独特能力, 自发现以来, 被广泛应用于众多复杂分子的合成. 通过对天然产物生物合成途径的理性分析, 将Wagner-Meerwein重排反应巧妙地引入到合成设计中, 能够快速、高效地构建常规手段难以实现的环系结构, 尤其是包含多个连续季碳手性中心的多环天然产物. 近年来, Wagner-Meerwein重排反应在萜类和甾体类天然产物合成中的应用日益增多, 展现了其独特的合成优势. 主要综述了2019年以来Wagner-Meerwein重排反应在这些复杂天然产物合成中的最新应用进展, 突显其在构建带有季碳手性中心的环系所发挥的独特优势.

关键词: Wagner-Meerwein重排, 天然产物, 全合成, 萜类, 甾体

The Wagner-Meerwein rearrangement reaction, renowned for its unique capability in efficiently constructing quaternary chiral centers and achieving carbon skeleton rearrangement within molecules, has been widely applied in the synthesis of numerous complex molecules since its discovery. By incorporating rational biosynthetic pathway analyses, the Wagner- Meerwein rearrangement can be ingeniously introduced into synthetic design to rapidly and efficiently construct ring systems that are challenging to achieve through conventional methods, particularly polycyclic natural products with multiple contiguous quaternary carbon stereocenters. In recent years, the application of the Wagner-Meerwein rearrangement in the synthesis of terpenoids and steroids has increased significantly, demonstrating its unique synthetic advantages. The latest applications of the Wagner-Meerwein rearrangement in the synthesis of these complex natural products since 2019 are primarily summarized, highlighting its distinct advantages in constructing ring systems with quaternary carbon chiral centers.

Key words: Wagner-Meerwein rearrangement, natural product, total synthesis, terpenoid, steroid

引用此文

陈杰, 李俊, 龙先文, 申海香, 邓军. Wagner-Meerwein重排反应在天然产物全合成中的应用[J]. 有机化学, 2025, 45(3): 896-912.

Jie Chen, Jun Li, Xianwen Long, Haixiang Shen, Jun Deng. Recent Advances of Wagner-Meerwein Rearrangement in Natural Product Synthesis[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 896-912.

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图/表 20

图式1. 羊毛甾醇生物合成过程中的Wagner-Meerwein重排反应

Scheme 1. Wagner-Meerwein rearrangement in the biosynthesis of lanosterol

图1. Wagner-Meerwein重排发展历史

Figure 1. Phylogeny of Wagner-Meerwein rearrangement

图式2. 杨震课题组的spirochensilide A全合成

Scheme 2. Total synthesis of spirochensilide A by Yang group

图式3. Heretsch课题组的spirochensilide A生源合成

Scheme 3. Biogenesis-inspired synthesis of spirochensilide A by Heretsch group

图式4. 邓军课题组的spirochensilide A生源合成

Scheme 4. Bioinspired synthesis of spirochensilide A by Deng group

图式5. 桂敬汉课题组的propindilactone G生源合成

Scheme 5. Bioinspired synthesis of propindilactone G by Gui group

图式6. 董广彬课题组的(?)-phainanoid A不对称全合成

Scheme 6. Asymmetric total synthesis of (?)-phainanoid A by Dong group

图式7. 丁寒锋课题组的(-)-pavidolide不对称全合成

Scheme 7. Asymmetric total synthesis of (-)-pavidolide by Ding group

图式8. 罗佗平课题组的(–)-oridonin不对称全合成

Scheme 8. Asymmetric total synthesis of (–)-oridonin by Luo group

图式9. 罗佗平课题组的木藜芦烷二萜对映选择性全合成

Scheme 9. Enantioselective total synthesis of grayanane diterpenoids by Luo group

图式10. 罗佗平课题组的(+)-kalmanol不对称全合成

Scheme 10. Asymmetric total synthesis of (+)-kalmanol by Luo group

图式11. 贾彦兴课题组的(+)-kalmanol不对称全合成

Scheme 11. Asymmetric total synthesis of (+)-kalmanol by Jia group

图式12. 丁寒锋课题组的rhodomolleins XIV和XLII不对称全合成研究

Scheme 12. Synthetic study toward rhodomolleins XIV and XLII by Ding group

图式13. 邓军课题组和普诺•白玛丹增课题组对rugosiformisin A的不对称全合成

Scheme 13. Asymmetric total synthesis of rugosiformisin A by Deng and Puno group

图式14. 涂永强课题组的(–)-phomopsene全合成

Scheme 14. Total synthesis of (–)-phomopsene by Tu group

图式15. Rychnovsky课题组的(–)-illisimonin A全合成

Scheme 15. Total synthesis of (–)-illisimonin A by Rychnovsky group

图式16. Kalesse课题组的(–)-illisimonin A不对称全合成

Scheme 16. Asymmetric total synthesis of (–)-illisimonin A by Kalesse group

图式17. 桂敬汉课题组的bufospirostenin A克级合成

Scheme 17. Gram-scale synthesis of bufospirostenin A by Gui group

图式18. 桂敬汉课题组的pinnigorgiols B和E简洁合成

Scheme 18. Concise synthesis of pinnigorgiols B and E by Gui group

图式19. Heretsch课题组的asperfloketals A~B合成

Scheme 19. Efficient synthesis of asperfloketals A~B by Heretsch group

参考文献 54

[1]	(a) Hong, B.-C.; Corey, E. J. J. Am. Chem. Soc. 1994, 116, 3149.
	(b) Waizumi, N.; Stankovic, A. R.; Rawal, V. H. J. Am. Chem. Soc. 2003, 125, 13022.
	(c) Kingsbury, J. S.; Corey, E. J. J. Am. Chem. Soc. 2005, 127, 13813.
	(d) Angeles, A. R.; Waters, S. P.; Danishefsky, S. M. J. Am. Chem. Soc. 2008, 130, 13765.
	(e) Gong, J.-X.; Lin, G.; Sun, W.-B.; Li, C.-C.; Yang, Z. J. Am. Chem. Soc. 2010, 132, 16745.
	(f) Jørgensen, L.; McKerrall, S. J.; Kuttruff, C. A.; Ungeheuer, F.; Felding, J.; Baran, P. S. Science 2013, 341, 878.
	(g) Cernijenko, A.; Risgaard, R.; Baran, P. S. J. Am. Chem. Soc. 2016, 138, 9425.
[2]	(a) Song, Z.-L.; Fan, C.-A.; Tu, Y.-Q. Chem. Rev. 2011, 111, 7523.
	(b) Naredla, R. R.; Klumpp, D. A. Chem. Rev. 2013, 113, 6905.
	(c) Wang, S.-H.; Li, B.-S.; Tu, Y.-Q. Chem. Commun. 2014, 50, 2393.
	(d) Zhang, X.-M.; Tu, Y.-Q.; Zhang, F.-M.; Chen, Z.-H.; Wang, S.-H. Chem. Soc. Rev. 2017, 46, 2272.
	(e) Wu, H.; Wang, Q.; Zhu, J.-P. Eur. J. Org. Chem. 2019, 10, 1964.
	(f) Zhang, X.-M.; Li, B.-S.; Wang, S.-H.; Zhang, K.; Zhang, F.-M.; Tu, Y.-Q. Chem. Sci. 2021, 12, 9262.
	(g) Delayre, B.; Wang, Q.; Zhu, J.-P. ACS Cent. Sci. 2021, 7, 559.
	(h) Zhang, Z.-L.; Qian, X.; Gu, Y.-C.; Gui, J.-H. Nat. Prod. Rep. 2024, 41, 251.
[3]	(a) Tantillo, D. J. Nat. Prod. Rep. 2011, 28, 1035.
	(b) Tantillo, D. J. Chem. Soc. Rev. 2010, 39, 2847.
	(c) de la Torre, M. C.; Sierra, M. A. Angew. Chem., Int. Ed. 2004, 43, 160.
	(d) Yoder, R. A.; Johnston, J. N. Chem. Rev. 2005, 105, 4730.
	(e) Wendt, K. U. Angew. Chem., Int. Ed. 2005, 44, 3966.
	(f) Abe, I. Nat. Prod. Rep. 2007, 24, 1311.
[4]	(a) Birladeanu, L. J. Chem. Educ. 2000, 77, 858.
	(b) Fittig, R. Liebigs Ann. Chem. 1860, 114, 54.
	(c) Butlerov, A.-M. Liebigs Ann. Chem. 1874, 174, 125.
	(d) Wagner, G.; Brickner, W. Chem. Ber. 1899, 32, 2302.
	(e) Meerwein, H.; van Emster, K. Chem. Ber. 1922, 55, 2500.
[5]	Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis, Elsevier Acad. Press, Burlington, 2005, p. 757.
[6]	Hanson, J. R. In Comprehensive Organic Synthesis, Vol. 3, Eds.: Trost, B. M.; Fleming, I., Oxford, Bighton, 1991, p. 705.
[7]	Zhao, Q.-Q.; Song, Q.-Y.; Jiang, K.; Li, G.-D.; Wei, W.-J.; Li, Y.; Gao, K. Org. Lett. 2015, 17, 2760.
[8]	Liang, X.-T.; Chen, J.-H.; Yang, Z. J. Am. Chem. Soc. 2020, 142, 8116.
[9]	(a) Alekseychuk, M.; Adrian, S.; Heinze, R. C.; Heretsch, P. J. Am. Chem. Soc. 2022, 144, 11574.
	(b) Long, X.-W.; Li, J.; Gao, F.; Wu, H.; Deng, J. J. Am. Chem. Soc. 2022, 144, 16292.
[10]	Pitzer, L.; Schwarz, J. L.; Glorius, F. Chem. Sci. 2019, 10, 8285.
[11]	Wappes, E. A.; Fosu, S. C.; Chopko, T. C.; Nagib, D. A. Angew. Chem., Int. Ed. 2016, 55, 9974.
[12]	Chen, M. S.; White, M. C. Science 2007, 318, 783.
[13]	(a) Compain, P.; Vatèle, J.-M.; Goré, J. Synlett 1994, 943.
	(b) Compain, P.; Goré, J.; Vatèle, J.-M. Tetrahedron 1996, 52, 10405.
[14]	Yang, D.; Wong, M.-K.; Wang, X.-C.; Tang, Y.-C. J. Am. Chem. Soc. 1998, 120, 6611.
[15]	(a) Xiao, W.-L.; Li, R.-T.; Huang, S.-X.; Pu, J.-X.; Sun, H.-D. Nat. Prod. Rep. 2008, 25, 871.
	(b) Shi, Y.-M.; Xiao, W.-L.; Pu, J.-X.; Sun, H.-D. Nat. Prod. Rep. 2015, 32, 367.
[16]	Lei, C.; Huang, S.-X.; Chen, J.-J.; Yang, L.-B.; Xiao, W.-L.; Chang, Y.; Lu, Y.; Huang, H.; Pu, J.-X.; Sun, H.-D. J. Nat. Prod. 2008, 71, 1228.
[17]	Wang, Y.; Chen, B.; He, X.-B.; Gui, J.-H. J. Am. Chem. Soc. 2020, 142, 5007.
[18]	Mitsunobu, O. Synthesis 1981, 1.
[19]	Breslow, R.; Corcoran, R.-J.; Snider, B.-B.; Doll, R.-J.; Khanna, P.-L.; Kaleya, R. J. Am. Chem. Soc. 1977, 99, 905.
[20]	Barton, D. H. R.; Budhiraja, R. P.; McGhie, J. F. J. Chem. Soc. C 1969, 336.
[21]	Fan, Y.-Y.; Zhang, H.; Zhou, Y.; Liu, H.-B.; Tang, W.; Zhou, B.; Zuo, J.-P.; Yue, J.-M. J. Am. Chem. Soc. 2015, 137, 138.
[22]	(a) Xie, J.-X.; Liu, X.; Zhang, N.; Choi, S.; Dong, G.-B. J. Am. Chem. Soc. 2021, 143, 19311.
	(b) Xie, J.-X.; Zheng, Z.; Liu, X.; Zhang, N.; Choi, S.; Dong, G.-B. J. Am. Chem. Soc. 2023, 145, 4828.
[23]	Sicinski, R. R.; Szczepek, W. J. Tetrahedron Lett. 1987, 28, 5729.
[24]	Shen, S.; Zhu, H.-J.; Chen, D.-W.; Liu, D.; Ofwegen, L.; Proksch, P.; Lin, W.-H. Tetrahedron Lett. 2012, 53, 5759.
[25]	He, C.; Xuan, J.; Rao, P.-R.; Xie, P.-P.; Hong, X.; Lin, X.-F.; Ding, H.-F. Angew. Chem., Int. Ed. 2019, 58, 5100.
[26]	Narasaka, K.; Soai, K.; Aikawa, Y.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1976, 49, 779.
[27]	Bal, S. A.; Marfat, A.; Helquist, P. J. Org. Chem. 1982, 47, 5045.
[28]	Kozmin, S. A.; Janey, J. M.; Rawal, V. H. J. Org. Chem. 1999, 64, 3039.
[29]	Fujita, E.; Fujita, T.; Katayama, H.; Shibuya, M. Chem. Commun. 1967, 252.
[30]	Kong, L.; Su, F.; Yu, H.; Jiang, Z.; Lu, Y.-D.; Luo, T.-P. J. Am. Chem. Soc. 2019, 141, 20048.
[31]	Giese, S.; Kastrup, L.; Stiens, D.; West, F. G. Angew. Chem., Int. Ed. 2000, 39, 1970.
[32]	Li, C.-J.; Liu, H.; Wang, L.-Q.; Jin, M.-W.; Chen, S.-N.; Bao, G.-H.; Qin, G.-W. Acta Chim. Sinica 2003, 61, 1153. (in Chinese)
	(李灿军, 刘慧, 陈绍农, 汪礼权, 金满文, 鲍官虎, 秦国伟, 化学学报, 2003, 61, 1153.)
[33]	Kong, L.; Yu, H.; Deng, M.-P.; Wu, F.-R.; Jiang, Z.; Luo, T.-P. J. Am. Chem. Soc. 2022, 144, 5268.
[34]	Lee, J. H. Tetrahedron 2020, 76, 131351.
[35]	Kong, L.; Yu, H.; Deng, M.-P.; Wu, F.-R.; Chen, S.-C.; Luo, T.-P. J. Org. Chem. 2023, 88, 6017.
[36]	Cheng, H.; Ma, T.-H.; Liu, X.; Jia, Y.-X. CCS Chem. 2024, 6, 2741.
[37]	Yang, Z.-N.; Rao, H.-J.-Z.; Yin, Y.-H.; Mu, S.; Jia, Z.-Q.; Ding, H.-F. Org. Lett. 2024, 26, 3524.
[38]	Wang, B.; Jiang, H.-Y.; Yang, J.; Li, J.; Yan, B.-C.; Chen, X.; Hu, K.; Li, X.-R.; Sun, H.-D.; Deng, J.; Puno, P.-T. Org. Lett. 2022, 24, 8104.
[39]	Toyomasu, T.; Kaneko, A.; Tokiwano, T.; Kanno, Y.; Kanno, Y.; Niida, R.; Miura, S.; Nishioka, T.; Ikeda, C.; Mitsuhashi, W.; Dairi, T.; Kawano, T.; Oikawa, H.; Kato, N.; Sassa, T. J. Org. Chem. 2009, 74, 1541.
[40]	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.
[41]	Wang, Y.-P.; Fang, K.; Tu, Y.-Q.; Yin, J.-J.; Zhao, Q.; Ke, T. Nat. Commun. 2022, 13, 2335.
[42]	Gui, J.-H.; Wang, Y.; Tian, H.-L.; Gao, Y.-Q.; Tian, W.-S. Tetrahedron Lett. 2014, 55, 4233.
[43]	Ma, S.-G.; Li, M.; Lin, M.-B.; Li, L.; Liu, Y.-B.; Qu, J.; Li, Y.; Wang, X.-J.; Wang, R.-B.; Xu, S.; Hou, Q.; Yu, S.-S. Org. Lett. 2017, 19, 6160.
[44]	Burns, A. S.; Rychnovsky, S. D. J. Am. Chem. Soc. 2019, 141, 13295.
[45]	Etling, C.; Tedesco, G.; Di Marco, A.; Kalesse, M. J. Am. Chem. Soc. 2023, 145, 7021.
[46]	Tian, H.-Y.; Ruan, L.-J.; Yu, T.; Zheng, Q.-F.; Chen, N.-H.; Wu, R.-B.; Zhang, X.-Q.; Wang, L.; Jiang, R.-W.; Ye, W.-C. J. Nat. Prod. 2017, 80, 1182.
[47]	Wang, Y.; Tian, H.-L.; Gui, J.-H. J. Am. Chem. Soc. 2021, 143, 19576.
[48]	Chang, Y.-C.; Kuo, L.-M.; Su, J.-H.; Hwang, T.-L.; Kuo, Y.-H.; Lin, C.-S.; Wu, Y.-C.; Sheu, J.-H.; Sung, P.-J. Tetrahedron 2016, 72, 999.
[49]	Li, X.-H.; Zhang, Z.-L.; Fan, H.-F.; Miao, Y.-L.; Tian, H.-L.; Gu, Y.-C.; Gui, J.-H. J. Am. Chem. Soc. 2021, 143, 4886.
[50]	Crich, D.; Yao, Q. J. Org. Chem. 1996, 61, 3566.
[51]	Jiao, F.-R. Gu, B.-B.; Zhu, H.-R.; Zhang, Y.; Liu, K.-C.; Zhang, W.; Han, H.; Xu, S.-H.; Lin, H.-W. J. Org. Chem. 2021, 86, 10954.
[52]	Alekseychuk, M.; Heretsch, P. J. Am. Chem. Soc. 2022, 144, 21867.
[53]	Heinze, R. C.; Lentz, D.; Heretsch, P. Angew. Chem., Int. Ed. 2016, 55, 11656.
[54]	(a) Kaib, P. S. J.; Schreyer, L.; Lee, S.; Properzi, R.; List, B. Angew. Chem., Int. Ed. 2016, 55, 13200.
	(b) Schreyer, L.; Properzi, R.; List, B. Angew. Chem., Int. Ed. 2019, 58, 777.
	(c) Wakchaure, V. N.; DeSnoo, W.; Laconsay, C. J.; Leutzsch, M.; Tsuji, N.; Tantillo, D. J.; List, B. Nature 2024, 625, 287.

Wagner-Meerwein重排反应在天然产物全合成中的应用

Recent Advances of Wagner-Meerwein Rearrangement in Natural Product Synthesis

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