利用自由基介导的乙烯基氨化反应合成石松生物碱锯齿嗪 A，制备β-锡烯胺连接子。
Total synthesis of the Lycopodium alkaloid serratezomine A using free radical-mediated vinyl amination to prepare a β-stannyl enamine linchpin.
机构信息
Department of Chemistry & Vanderbilt Institute of Chemical Biology, Vanderbilt University, Nashville, Tennessee 37235-1822, USA.
出版信息
J Org Chem. 2013 Feb 1;78(3):822-43. doi: 10.1021/jo302333s. Epub 2012 Dec 28.
Abstract
Serratezomine A is a member of the structurally diverse class of compounds known as the Lycopodium alkaloids. The key supporting studies and successful total synthesis of serratezomine A are described in this account. Significant features of the synthesis include the first application of free radical mediated vinyl amination and Hwu's oxidative allylation in a total synthesis and an intramolecular lactonization via a transannular S(N)i reaction. Minimal use of protecting groups and the highly diastereoselective formation of a hindered, quaternary stereocenter using an umpolung allylation are also highlights from a strategy perspective. Observation of quaternary carbon epimerization via a retro-Mannich/Mannich sequence highlights the additional challenge presented by the axial alcohol at C8 in serratezomine A.
摘要
锯齿天冬酰胺 A 是结构多样的石松生物碱类化合物的成员。本报告描述了锯齿天冬酰胺 A 的关键支持研究和成功的全合成。该合成的显著特点包括自由基介导的乙烯基氨化和 Hwu 的氧化烯丙基化在全合成中的首次应用，以及通过反环 S（N）i 反应进行分子内内酯化。从策略的角度来看，最小化使用保护基团和使用反转亲核烷基化高度非对映选择性地形成受阻的季立体中心也是亮点。通过反曼尼希/曼尼希序列观察到季碳原子差向异构化突出了锯齿天冬酰胺 A 中 C8 处轴向醇带来的额外挑战。
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