Chinese Journal of Organic Chemistry >
Asymmetric Total Synthesis and Structural Revision of Antiangiogenic Natural Product Penduliflaworosin
Received date: 2024-09-20
Revised date: 2024-10-31
Online published: 2024-12-06
Supported by
National Natural Science Foundation of China(22071030); National Natural Science Foundation of China(22222104); Science and Technology Commission of Shanghai Municipality(22JC1401102)
Penduliflaworosin is a diterpenoid natural product isolated from the medicinal plant Croton crassifolius, which demonstrates highly potent antiangiogenic activities. In this work, enantioselective total synthesis of penduliflaworosin and its C4 epimer has been realized for the first time, thus revising the erroneous structure of penduliflaworosin shown in previous literatures. In the synthesis, the main cis-decalin moiety bearing two quaternary stereogenic centers was efficiently constructed by tandem olefin migration/asymmetric inverse-electron-demand Diels-Alder reaction of 2-pyrone with polysubstituted 1,4- cyclohexadiene. From this intermediate, enantioselective synthesis of penduliflaworosin and its epimer was realized by subsequent several key steps, involving the 1,2-addition with 3-furanyl zinc reagent, oxidation, and olefin isomerization.
Xuge Si , Quan Cai . Asymmetric Total Synthesis and Structural Revision of Antiangiogenic Natural Product Penduliflaworosin[J]. Chinese Journal of Organic Chemistry, 2025 , 45(3) : 959 -968 . DOI: 10.6023/cjoc202409025
| [1] | Zhu, Y.-K.; Hu, Y.; Cheng, N.; Cen, Y.-Z. Chin. Tradit. Herb. Drugs 2013, 44, 1231. (in Chinese) |
| [1] | (朱耀魁, 胡颖, 程妮, 岑颖洲, 中草药, 2013, 44, 1231.) |
| [2] | Meng, J.; Liang, S.-W.; Wang, B.-L.; Wang, S.-M. J. Guangdong Pharm. Univ. 2014, 30, 385. (in Chinese) |
| [2] | (孟江, 梁生旺, 王佰灵, 王淑美, 广东药科大学学报, 2014, 30, 385.) |
| [3] | Roncero, A. M.; Tobal, I. E.; Moro, R. F.; Díez, D.; Marcos, I. S. Nat. Prod. Rep. 2018, 35, 955. |
| [4] | (a) Yuan, Q.-Q.; Tang, S.; Song, W.-B.; Wang, W.-Q.; Huang, M.; Xuan, L.-J. J. Nat. Prod. 2017, 80, 254. |
| [4] | (b) Qiu, M.-S.; Cao, D.; Gao, Y.-H.; Li, S.-H.; Zhu, J.-P.; Yang, B.; Zhou, L.; Zhou, Y.; Jin, J.; Zhao, Z.-X. Fitoterapia 2016, 108, 81. |
| [5] | Liu, C.; Zhang, R.-R.; Niu, Q.-L.; Zhang, J.; Wang, M.-X.; Meng, N.-N.; Wang, Q.; Sun, J.-Y.; Wang, W.-L. Nat. Prod. Res. 2021, 35, 4479. |
| [6] | Li, C.; Sun, X.; Yin, W.; Zhan, Z.; Tang, Q.; Wang, W.; Zhuo, X.; Wu, Z.; Zhang, H.; Li, Y.; Zhang, Y.; Wang, G. Front. Chem. 2021, 9, 733350. |
| [7] | Ye, G. H.; Xue, J. J.; Liang, W. L.; Yang, S. J. Nat. Prod. Res. 2019, 35, 1421. |
| [8] | Wang, G.-C.; Li, J.-G.; Li, G.-Q.; Xu, J.-J.; Wu, X.; Ye, W.-C.; Li, Y.-L. J. Nat. Prod. 2012, 75, 2188. |
| [9] | Wang, J.-J.; Chung, H. Y.; Zhang, Y.-B.; Li, G.-Q.; Li, Y.-L.; Huang, W.-H.; Wang, G.-C. Phytochemistry 2016, 122, 270. |
| [10] | Liang, Y.; Zhang, Y.; Wang, G.; Li, Y.; Huang, W. Molecules 2017, 22, 126. |
| [11] | (a) Si, X.-G.; Zhang, Z.-M.; Zheng, C.-G.; Li, Z.-T.; Cai, Q. Angew. Chem., Int. Ed. 2020, 59, 18412. |
| [11] | (b) Zhang, Z.-M.; Zhang, J.; Cai, Q. Chem. Sci. 2023, 14, 12598. |
| [12] | Si, X.-G.; Feng, S.-X.; Wang, Z.-Y.; Chen, X.; Xu, M.-M.; Zhang, Y.-Z.; He, J.-X.; Yang, L.; Cai, Q. Angew. Chem., Int. Ed. 2023, 62, e202303876. |
| [13] | (a) Adesogan, E. K. J. Chem. Soc., Perkin Trans. 1. 1 1981, 1151. |
| [13] | (b) Mbwambo, Z. H.; Foubert, K.; Chacha, M.; Kapingu, M. C.; Magadula, J. J.; Moshi, M. M.; Lemière, F.; Goubitz, K.; Fraanje, J.; Peschar, R.; Vlietinck, A.; Apers, S.; Pieters, L. Planta Med. 2009, 75, 262. |
| [14] | Sanni, S. B.; Behm, H.; Beurskens, P. T.; Adesogan, E. K. Acta Cryst. C 1987, 43, 555. |
/
| 〈 |
|
〉 |
