Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
J Am Chem Soc. 2011 Jan 19;133(2):214-9. doi: 10.1021/ja109531d. Epub 2010 Dec 17.
A devised biomimetic strategy toward the C'D'E'F' domain (6) of maitotoxin (1) led to hydroxy triepoxide 8 as a postulated polyepoxide precursor. However, all attempts to induce the desired cascade to form the targeted compound through a zip-type reaction under neutral or acidic conditions failed, prompting adoption of a linear stepwise approach to 6. The successful synthetic strategy for the synthesis of the C'D'E'F' domain of maitotoxin commenced from furfuryl alcohol (11), proceeded through F' ring building block 15, and involved two regio- and stereoselective intramolecular hydroxy epoxide openings and a stereoselective SmI(2)-mediated ring closure to forge rings C', E', and D', respectively. (13)C NMR spectroscopic analysis of the synthesized domain (6) and comparisons with previous results confirmed the original structural assignment of this region of maitotoxin. X-ray crystallographic analysis of 6 provided unambiguous proof of its structure.
一种针对海兔毒素（1）的 C'D'E'F' 结构域（6）的仿生设计策略导致了羟基三环氧 8 作为假定的多环氧前体。然而，所有试图通过中性或酸性条件下的 zip 型反应诱导所需级联反应以形成目标化合物的尝试都失败了，这促使我们采用线性逐步方法来合成 6。海兔毒素 C'D'E'F' 结构域的成功合成策略始于糠醇（11），经过 F' 环构建块 15，并涉及两个区域和立体选择性的分子内羟基环氧化物开环和立体选择性的 SmI(2)介导的环合，分别形成 C'、E'和 D'环。（13）C NMR 光谱分析合成的结构域（6）并与以前的结果进行比较，证实了该区域海兔毒素的原始结构分配。6 的 X 射线晶体学分析提供了其结构的明确证据。
