Total synthesis of atropurpuran.
Total synthesis of atropurpuran.
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阿托紫珀兰的全合成
DOI：
10.1038/ncomms12183
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发表时间：
2016-07-08
影响因子：
16.6
通讯作者：
Qin Y
中科院分区：
文献类型：
--
作者：
Gong J;Chen H;Liu XY;Wang ZX;Nie W;Qin Y
由于它们的结构复杂性和生物学意义，多环二萜及其生物遗传相关生物碱的合成在过去几十年中一直是相当感兴趣的主题，进展包括几个难以捉摸的目标的令人印象深刻的合成。尽管付出了巨大的努力，但征服这个庞大的天然产物家族的独特结构类型仍然是一个长期的挑战。带有稠合四环[5.3.3.04，9.04，12]十三烷单元的Arcutane二萜和相关生物碱包括在这些未解之谜中。本文报道了这些分子的核心结构的构建和（±）-atropuran的首次全合成。合成的主要特征包括氧化脱芳构化/分子内Diels-Alder环加成级联，顺序的羟醛和酮基-烯烃环化以组装高度笼状骨架，以及化学选择性和立体选择性还原以在目标分子中安装必需的烯丙基羟基。
Due to their architectural intricacy and biological significance, the synthesis of polycyclic diterpenes and their biogenetically related alkaloids have been the subject of considerable interest over the last few decades, with progress including the impressive synthesis of several elusive targets. Despite tremendous efforts, conquering the unique structural types of this large natural product family remains a long-term challenge. The arcutane diterpenes and related alkaloids, bearing a congested tetracyclo[5.3.3.04,9.04,12]tridecane unit, are included in these unsolved enigmas. Here we report a concise approach to the construction of the core structure of these molecules and the first total synthesis of (±)-atropurpuran. Pivotal features of the synthesis include an oxidative dearomatization/intramolecular Diels-Alder cycloaddition cascade, sequential aldol and ketyl-olefin cyclizations to assemble the highly caged framework, and a chemoselective and stereoselective reduction to install the requisite allylic hydroxyl group in the target molecule.