不对称的阿尔库丁丁,阿尔库丁和阿尔库丁的总合成
Shupeng Zhou1, Kaifu Xia1, Xuebing Leng2
1State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences , Chinese Academy of Sciences , 345 Lingling Road , Shanghai 200032 , China.
Journal of the American Chemical Society
|July 6, 2019
概括
研究人员实现了三种C20-diterpenoid类化合物的不对称总合成:阿库丁丁,阿库丁和阿库丁. 关键步骤包括迪尔斯-阿尔德反应和普林斯循环/瓦格纳-梅尔维恩重组级联,用于构建核心结构.
科学领域:
- 有机化学
- 自然产品合成
- 化物化学
背景情况:
- 迪特类类是具有多种生物活性的重要自然产品.
- 具有C20-diterpenoid骨架的阿尔库丁类类化合物具有复杂的合成挑战.
- 了解这些复杂分子的立体化学对于结构-活性关系研究至关重要.
研究的目的:
- 实现第一个不对称的阿库丁丁,阿库丁丁和阿库丁的总合成.
- 开发高效的合成策略来构建这些化合物的五环核.
- 确认关键立体中心的绝对配置,特别是在上.
主要方法:
- 使用两个迪尔斯-阿尔德反应快速组装五环中间体.
- 开发了一种涉及普林斯循环和瓦格纳-梅尔维恩重组的级联序列,以构建阿库丁丁核.
- 采用化学选择性降解性氨基化和自发性氨基形成以构建皮罗林基因.
主要成果:
- 成功合成了阿库丁丁,阿库丁丁和阿库丁.
- 建立了一个可扩展的氧化五环中间体路径.
- 通过合成和X射线结晶学证实了arcutine中的α-碳的 (S) 配置.
结论:
- 开发的合成策略提供了有效的阿尔库丁类化物.
- 合成验证了构建复杂的五环二化框架的关键步骤.
- 已经确定了阿库丁的立体化学成分.
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