Total syntheses of (–)-macrocalyxoformins A and B and (–)-ludongnin C

Zichen Cao, Wenxuan Sun, Jingfu Zhang, Junming Zhuo, Shaoqiang Yang, Xiaocui Song, Yan Ma, Panrui Lu, Ting Han and Chao Li ()
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Zichen Cao: Peking University
Wenxuan Sun: National Institute of Biological Sciences
Jingfu Zhang: National Institute of Biological Sciences
Junming Zhuo: National Institute of Biological Sciences
Shaoqiang Yang: National Institute of Biological Sciences
Xiaocui Song: National Institute of Biological Sciences
Yan Ma: National Institute of Biological Sciences
Panrui Lu: National Institute of Biological Sciences
Ting Han: National Institute of Biological Sciences
Chao Li: National Institute of Biological Sciences

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract 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.

Date: 2024
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DOI: 10.1038/s41467-024-50374-1

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