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总的综合,结构修订,和绝对配置的 (-) -brevenal
Haruhiko Fuwa1, Makoto Ebine, Andrea J Bourdelais
1Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, Aoba-ku, Sendai 981-8555, Japan.
Journal of the American Chemical Society
|December 21, 2006
概括
研究人员实现了海洋聚乙烯天然产品布雷维纳尔的总合成. 结构分析显示,天然产品很可能是最初提出的结构的epimer,现在通过合成得到证实.
科学领域:
- 有机化学 有机化学
- 自然产品的合成自然产品的合成
- 海洋天然产品 海洋天然产品
背景情况:
- 布雷维纳尔是一种非有毒的多环乙烯天然产品,是从Karenia brevis.中分离出来的.
- 最初提出的布雷维纳的结构缺乏明确的立体化学赋值.
研究的目的:
- 为了实现Brevenal.的拟议结构的总合成.
- 根据光谱数据和合成,修订和确认布雷维纳尔的结构.
- 为了确定天然产品的绝对配置.
主要方法:
- 五环聚乙烯骨架的融合组装使用苏子-米亚乌拉合.
- 通过铜(I) 硫-2-碳酸盐 (CuTC) 促进的改性Stille合,对二醇侧链进行立体选择性构造.
- 合成化合物与天然产品之间的详细的NMR光谱比较.
主要成果:
- 完成了最初提出的结构 (1) 的总合成.
- 核磁共振谱的差异表明需要进行结构性修订.
- 自然产品被确定为拟议结构的C26表皮质 (2).
- 修订后的结构 (2) 通过其总合成进行了验证,证实了绝对配置.
结论:
- 布雷维纳尔及其表皮质的总合成提供了明确的结构和立体化学赋值.
- 这项工作修订了Brevenal的已知结构,这是一个重要的海洋聚乙烯.
- 开发的合成策略适用于其他复杂的多环乙烯天然产品.
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