PDF(Pubmed)
Abstract：
Clickable chemical tools are essential for studying the localization and role of biomolecules in living cells. For this purpose, alkyne-based close analogs of the respective biomolecules are of outstanding interest. Here, in the field of phytosterols, we present the first alkyne derivative of sitosterol, which fulfills the crucial requirements for such a chemical tool as follows: very similar in size and lipophilicity to the plant phytosterols, and correct absolute configuration at C-24. The alkyne sitosterol FB-DJ-1 was synthesized, starting from stigmasterol, which comprised nine steps, utilizing a novel alkyne activation method, a Johnson-Claisen rearrangement for the stereoselective construction of a branched sterol side chain, and a Bestmann-Ohira reaction for the generation of the alkyne moiety.
摘要：
可点击化学工具对于研究生物分子在活细胞中的定位和作用至关重要。为此,各个生物分子的基于炔烃的紧密类似物具有突出的兴趣。这里,在植物甾醇领域，我们介绍了谷甾醇的第一个炔烃衍生物，它满足了这种化学工具的关键要求如下：与植物甾醇的大小和亲脂性非常相似，和正确的绝对配置在C-24。合成了炔烃谷甾醇FB-DJ-1,从豆甾醇开始，包括九个步骤，利用一种新的炔烃活化方法，用于立体选择性构建支链甾醇侧链的Johnson-Claisen重排，和用于生成炔部分的Bestmann-Ohira反应。
