The first total synthesis of (±)-ingenol
The first total synthesis of (±)-ingenol
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DOI：
10.1021/ja026600a
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发表时间：
2002-08-21
影响因子：
15
通讯作者：
Jeon, YT
中科院分区：
文献类型：
--
作者：
Winkler, JD;Rouse, MB;Jeon, YT
首次实现了（±）-巨大戟二萜醇的全合成。该合成的关键特征包括使用高度非对映选择性的迈克尔反应来固定C-11甲基立体化学，以及通过非对映选择性卡宾加成将二甲基环丙烷并入Δ 13，14烯烃。分子内二氧杂环烯酮光加成-断裂序列导致关键的C-8/C-10反式桥头立体化学的建立，这是合成巨大戟烷的核心挑战。使用C-6α羟甲基作为氧化7个相邻碳中心的唯一手柄，合成得以完成。
The first total synthesis of (±)-ingenol has been achieved. The key features of the synthesis include the use of a highly diastereoselective Michael reaction to fix the C-11 methyl stereochemistry and the incorporation of the dimethylcyclopropane via diastereoselective carbene addition to the Δ13,14olefin. The intramolecular dioxenone photoaddition-fragmentation sequence leads to the establishment of the critical C-8/C-10 trans intrabridgehead stereochemistry, a central challenge in the synthesis of ingenanes. The completion of the synthesis proceeds using the C-6α hydroxymethyl group as the sole handle for oxidation of seven contiguous carbon centers.