基于氧化吡喃鎓盐的[5 + 2]环加成反应立体选择性全合成海南洛定醇和哈林通内酯。
Stereoselective total synthesis of hainanolidol and harringtonolide via oxidopyrylium-based [5 + 2] cycloaddition.
机构信息
School of Pharmacy, University of Wisconsin, Madison, Wisconsin 53705, USA.
出版信息
J Am Chem Soc. 2013 Aug 21;135(33):12434-8. doi: 10.1021/ja406255j. Epub 2013 Aug 9.
Abstract
The tetracyclic carbon skeleton of hainanolidol and harringtonolide was efficiently constructed by an intramolecular oxidopyrylium-based [5 + 2] cycloaddition. An anionic ring-opening strategy was developed for the cleavage of the ether bridge in 8-oxabicyclo[3.2.1]octenes derived from the [5 + 2] cycloaddition. Conversion of cycloheptadiene to tropone was realized by a sequential [4 + 2] cycloaddition, Kornblum-DeLaMare rearrangement, and double elimination. The biomimetic synthesis of harringtonolide from hainanolidol was also confirmed.
摘要
通过分子内氧化吡喃鎓基 [5 + 2] 环加成反应有效地构建了海南冬酰胺和哈林托内酯的四环碳骨架。开发了一种阴离子开环策略，用于裂解[5 + 2]环加成反应衍生的 8-氧杂双环[3.2.1]辛烷中的醚桥。通过顺序[4 + 2]环加成、Kornblum-DeLaMare 重排和双消除，实现了环庚二烯到吐罗酮的转化。还证实了从海南冬酰胺生物模拟合成哈林托内酯。
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