Total synthesis of (-)-sarain A.
Total synthesis of (-)-sarain A.
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DOI：
10.1002/anie.200600417
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发表时间：
2006-04
影响因子：
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通讯作者：
N. Garg;S. Hiebert;L. Overman
中科院分区：
文献类型：
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作者：
N. Garg;S. Hiebert;L. Overman
本文详细介绍了我们对复杂的海洋生物碱沙拉因A的合成研究，我们构思了各种策略，遇到了挫折，并开发了解决方案，最终导致了成功的对映选择性全合成。我们获得(−)-Sarain A的路线包括一系列关键步骤，包括安装C4‘−C3’−C7‘立体三元的不对称Michael加成，设置C3四元碳立体中心的环氧硅烷-N-磺酰亚胺离子环化，并组装二氮杂环十一烷核，闭环歧化反应以构建13元环，分子内Stille偶联以形成不饱和的14元大环，以及后期安装叔胺−醛邻近相互作用。
This article describes the details of our synthetic studies toward the complex marine alkaloid sarain A. Various strategies were conceived, setbacks encountered, and solutions developed, ultimately leading to a successful enantioselective total synthesis. Our route to (−)-sarain A features a number of key steps, including an asymmetric Michael addition to install the C4‘−C3‘−C7‘ stereotriad, an enoxysilane-N-sulfonyliminium ion cyclization to set the C3 quaternary carbon stereocenter, and assemble the diazatricycloundecane core, a ring-closing metathesis to construct the 13-membered ring, an intramolecular Stille coupling to fashion the unsaturated 14-membered macrocycle, and a late-stage installation of the tertiary amine−aldehyde proximity interaction.