Collective Total Syntheses of Atisane-Type Diterpenes and Atisine-Type Diterpenoid Alkaloids: (±)-Spiramilactone B, (±)-Spiraminol, (±)-Dihydroajaconine, and (±)-Spiramines C and D
Collective Total Syntheses of Atisane-Type Diterpenes and Atisine-Type Diterpenoid Alkaloids: (±)-Spiramilactone B, (±)-Spiraminol, (±)-Dihydroajaconine, and (±)-Spiramines C and D
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DOI：
10.1002/anie.201508996
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发表时间：
2016-01-04
影响因子：
16.6
通讯作者：
Wang, Feng-Peng
中科院分区：
文献类型：
--
作者：
Cheng, Hang;Zeng, Fan-Hao;Wang, Feng-Peng
首次报道了结构复杂的双烷型二萜和生物遗传相关的双环二萜类生物碱(+/-)-螺内酯B、(+/-)-螺氨醇、(+/-)-二氢雅克宁和(+/-)-螺胺C和D的全合成。合成的亮点包括螺内酯B的后期仿生转化，螺内酯E的五环骨架的简单的形式内酯迁移，高效和非对映选择性的1，7-烯炔环异构化以构建官能化的四环并二环骨架，以及串联的逆转录Diels-Alder/分子内Diels-Alder序列以获得三环-[6.2.2.0]环体系。
The first total syntheses of the architecturally complex atisane-type diterpenes and biogenetically related atisine-type diterpenoid alkaloids (+/-)-spiramilactone B, (+/-)-spiraminol, (+/-)-dihydroajaconine, and (+/-)-spiramines C and D are reported. Highlights of the synthesis include a latestage biomimetic transformation of spiramilactone B, a facile formal lactone migration from the pentacyclic skeleton of spiramilactone E, a highly efficient and diastereoselective 1,7-enyne cycloisomerization to construct the functionalized tetracyclic atisane skeleton, and a tandem retro-Diels-Alder/intramolecular Diels-Alder sequence to achieve the tricyclo-[6.2.2.0] ring system.