| Autor: |
Cao, Zichen, Sun, Wenxuan, Zhang, Jingfu, Zhuo, Junming, Yang, Shaoqiang, Song, Xiaocui, Ma, Yan, Lu, Panrui, Han, Ting, Li, Chao |
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| Zdroj: |
Nature Communications; 7/18/2024, Vol. 15 Issue 1, p1-10, 10p |
| Abstrakt: |
The complex and diverse molecular architectures along with broad biological activities of ent-kauranoids natural products make them an excellent testing ground for the invention of synthetic methods and strategies. Recent efforts notwithstanding, synthetic access to the highly oxidized enmein-type ent-kauranoids still presents considerable challenges to synthetic chemists. Here, we report the enantioselective total syntheses of C-19 oxygenated enmein-type ent-kauranoids, including (–)-macrocalyxoformins A and B and (–)-ludongnin C, along with discussion and study of synthetic strategies. The enabling feature in our synthesis is a devised Ni-catalyzed decarboxylative cyclization/radical-polar crossover/C-acylation cascade that forges a THF ring concomitantly with the β-keto ester group. Mechanistic studies reveal that the C-acylation process in this cascade reaction is achieved through a carboxylation followed by an in situ esterification. Biological evaluation of these synthetic natural products reveals the indispensable role of the ketone on the D ring in their anti-tumor efficacy. The complex and diverse molecular architectures along with broad biological activities of ent-kauranoids natural products attract increasing interest from synthetic chemists. Herein, the authors report the enantioselective total syntheses of C-19 oxygenated enmein-type ent-kauranoids, including (–)-macrocalyxoformins A and B and (–)-ludongnin C. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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