（+）-13-脱氧泰德内酯的全合成。

Total synthesis of (+)-13-deoxytedanolide.

作者信息

Julian Lisa D, Newcom Jason S, Roush William R

机构信息

Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.

出版信息

J Am Chem Soc. 2005 May 4;127(17):6186-7. doi: 10.1021/ja050729d.

DOI:10.1021/ja050729d

PMID:15853320

Abstract

A total synthesis of 13-deoxytedanolide is described. The synthesis features a highly stereoselective fragment assembly aldol reaction of methyl ketone 4 and aldehyde 5 to establish the complete carbon skeleton of the natural product in the form of aldol 15. The facile formation of the remarkably unreactive hemiketal 16 thwarted attempts to elaborate 15 to tedanolide. However, deoxygenation of the C(13)-hydroxyl of 16 provided the 13-deoxy hemiketal 17 that was smoothly elaborated to 13-deoxytedanolide.

摘要

本文描述了13-脱氧泰德内酯的全合成。该合成的特点是甲基酮4和醛5发生高度立体选择性的片段组装羟醛反应，以羟醛15的形式构建天然产物的完整碳骨架。极难反应的半缩酮16的轻松形成阻碍了将15转化为泰德内酯的尝试。然而，16的C(13)-羟基脱氧得到了13-脱氧半缩酮17，其顺利转化为13-脱氧泰德内酯。