Total syntheses of (±)-fawcettimine, (±)-fawcettidine, (±)-lycoflexine, and (±)-lycoposerramine-Q.
Total syntheses of (±)-fawcettimine, (±)-fawcettidine, (±)-lycoflexine, and (±)-lycoposerramine-Q.
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DOI：
10.1002/chem.201300364
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发表时间：
2013-06
期刊：
影响因子：
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通讯作者：
N. Itoh;T. Iwata;Hiromi Sugihara;F. Inagaki;C. Mukai
中科院分区：
文献类型：
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作者：
N. Itoh;T. Iwata;Hiromi Sugihara;F. Inagaki;C. Mukai
以高度立体选择性的方式完成了四种与fawcettimine相关的石松生物碱（±）-fawcettimine、（±）-fawcettidine、（±）-lycoposeramine-Q和（±）-lycoflexine的全合成。4-亚甲基-6-辛基-1-烯-7-炔的Pauson-Khand反应，然后区域选择性和立体选择性氢化，导致具有所需立体化学的带有甲基的双环[4.3.0]壬烯酮中间体的短步骤制备。随后的双环化合物的化学操作得到6-5-9-元三环二氧代化合物，然后以替代和更有效的方式将其转化为四种靶向生物碱。
The total syntheses of four fawcettimine-related Lycopodium alkaloids, (±)-fawcettimine, (±)-fawcettidine, (±)-lycoposerramine-Q, and (±)-lycoflexine, were completed in a highly stereoselective manner. The Pauson-Khand reaction of 4-methylidene-6-siloxyoct-1-en-7-yne followed by regio- and stereoselective hydrogenation led to the short-step preparation of the bicyclo[4.3.0]nonenone intermediate bearing a methyl group with the required stereochemistry. The subsequent chemical manipulation of the bicyclic compound afforded the 6-5-9-membered tricyclic dioxo compound, which was then transformed into the four targeted alkaloids in an alternative and more efficient fashion.