Recent Advances of Wagner-Meerwein Rearrangement in Natural Product Synthesis

doi:10.6023/cjoc202408010

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (3): 896-912.DOI: 10.6023/cjoc202408010 Previous Articles Next Articles

REVIEWS

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)

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 20

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

Figure 1. Phylogeny of Wagner-Meerwein rearrangement

Scheme 2. Total synthesis of spirochensilide A by Yang group

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

Scheme 4. Bioinspired synthesis of spirochensilide A by Deng group

Scheme 5. Bioinspired synthesis of propindilactone G by Gui group

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

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

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

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

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

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

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

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

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

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

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

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

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

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

References 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

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 20

References 54

Related Articles 15

Recommended Articles 0

Metrics

Comments

[1]	Tao Long, Shuzhong He, Chao Li. Research Progress on the Radical-Polar Crossover Reaction in Total Synthesis of Natural Products [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 748-763.
[2]	Haikang Mao, Jing Xu. Recent Progress in the Total Synthesis of Daphniphyllum Alkaloids [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 866-880.
[3]	Jiuzhou Yi, Liang Huo, Jinyan Chen, Meng Liu, Huilin Li, Xuegong She. Protecting Group Effects on the Total Syntheses of Several Classes of Natural Products [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 1030-1039.
[4]	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.
[5]	Chuang Li, Cheng Zhang, Xiaoyu Liu, Yong Qin. Recent Progress in the Total Synthesis of Diterpenoid Alkaloids [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 881-895.
[6]	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.
[7]	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.
[8]	Yunshan Li, Yuxin Zhang, Yefeng Tang. Recent Advance in the Synthesis of Tricyclic Marine Alkaloids: Cylindricines, Lepadiformines, and Fasicularin [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 837-851.
[9]	Zhiyu Gao, Xuena Lu, Yiqing Li, Li Ren, Hongdong Hao. Advances in the Total Synthesis of Ganoderma Meroterpenoids [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 814-836.
[10]	Long Meng, Jin-Bao Qiao, Yu-Ming Zhao. Progress on the Total Synthesis of Ryania Diterpenoids [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 804-813.
[11]	Kai Wang, Jiajun Sui, Chunhong Long, Songjuan Luo, Yongming Chuan, Hongbo Qin. Total Syntheses of Cochlearol F and Didehydroconicol by Biphenyl Boronic Acid [J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 343-348.
[12]	Shuai Yang, Jie Wu, Liangliang Wang. Asymmetric Total Synthesis towards the Simplified Analogs of Antibiotic Elansolid A [J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2350-2362.
[13]	Hongbo Zhu, Ji Wang, Weiyan Hu, Tang Zhou, Zhiqi Lin, Rongping Zhang, Chang'an Geng, Xinglong Chen. Diterpenoids with Cytotoxicity for Pancreatic Cancer SW1990 Cells from the Rhizomes of Euphorbia jolkinii Boiss [J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1929-1937.
[14]	Tianfeng Peng, Yuxiang Zhao, Shaojian Pu, Juan Luo, Teng Liu, Yingchun Miao, Xianfu Shen. Recent Advances in Total Synthesis of Prenylated Indole Alkaloids by Transition Metal-Catalyzed Reactions as the Key Step [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1160-1180.
[15]	Junyi Li, Lu Yang, Mingbin Chen, Yong Rao, Zhongping Jiang, Ling Huang. Diterpenoids from Mangrove Plant Excoecaria agallocha L. and Their Anti-neuroinflammatory Activities [J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3526-3530.