Total Synthesis of (–)-Daphnezomines A and B,Journal of the American Chemical Society

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Total Synthesis of (–)-Daphnezomines A and B
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-08-19 , DOI: 10.1021/jacs.0c06717
Guangpeng Xu _{1,

2} , Jinbao Wu ₂ , Luyang Li ₂ , Yunan Lu ₂ , Chao Li _{2,

3}

Affiliation

Daphnezomines A and B are structurally unusual Daphniphyllum alkaloids that contain a unique aza-adamantane core skeleton. Herein, a modular approach to these alkaloids is presented that exploits a diverse array of reaction strategies. Commencing from a chiral pool terpene-(S)-carvone, the azabicyclo[3.3.1]nonane backbone, which occurs widely in Daphniphyllum alkaloids, was easily accessed through a Sharpless allylic amination and a palladium-catalyzed oxidative cyclization. A protecting group enabled a stereoselective B-alkyl Suzuki-Miyaura coupling sequence, and an Fe-mediated hydrogen atom transfer (HAT)-based radical cyclization were then applied to construct C6 and C8 stereocenters. A final epimer locking strategy enabled the assembly of the highly congested aza-adamantane core, thereby achieving the first total synthesis of (-)-daphnezomines A and B in 14 steps.

中文翻译：

(-)-Daphnezomines A 和 B 的全合成

Daphnezomines A 和 B 是结构不寻常的 Daphniphyllum 生物碱，包含独特的氮杂金刚烷核心骨架。在此，提出了一种利用多种反应策略来处理这些生物碱的模块化方法。从手性池萜烯-(S)-香芹酮开始，氮杂双环 [3.3.1] 壬烷主链广泛存在于水蚤生物碱中，可通过 Sharpless 烯丙基胺化和钯催化的氧化环化轻松获得。保护基团启用立体选择性 B-烷基 Suzuki-Miyaura 偶联序列，然后应用基于 Fe 介导的氢原子转移 (HAT) 的自由基环化来构建 C6 和 C8 立体中心。最终的差向异构体锁定策略能够组装高度拥挤的氮杂金刚烷核心，

更新日期：2020-08-19

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