Institute of Organic Chemistry, University of Vienna, Währingerstrasse 38, 1090 Vienna, Austria.
Chemistry. 2010 Jan 11;16(2):507-19. doi: 10.1002/chem.200902226.
Two convergent total syntheses of the ansa-polyketide (-)-kendomycin (1) are described. The syntheses benefit from the use of readily available and cheap starting materials. Highly complex diastereoselective Claisen-Ireland rearrangements were used to introduce the (E)-double bond and the C16-Me group. The ring closure of the strained ansa macrocycle was achieved by ring-closing metathesis and a highly efficient combination of macrolactonization and photo-Fries reaction. A protecting group free endgame via an unstable o-quinone is presented. Additionally some unsuccessful synthetic efforts towards the total synthesis of 1 are described.
描述了两种会聚的ansa-聚酮（-）-肯德霉素（1）的全合成。这些合成方法受益于使用易得且廉价的起始材料。高度复杂的非对映选择性Claisen-Ireland 重排被用于引入（E）-双键和 C16-Me 基团。张力ansa 大环的环合通过闭环复分解和大环内酯化与光Fries 反应的高效组合来实现。通过不稳定的邻醌呈现了一种无保护基的末端策略。此外，还描述了一些针对 1 的全合成的不成功的合成尝试。
