Synthesis and absolute stereochemical assignment of (+)-miyakolide

被引：82

作者：

Evans, DA ^{[1
]}

Ripin, DHB ^{[1
]}

Halstead, DP ^{[1
]}

Campos, KR ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Biol Chem, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1999年 / 121卷 / 29期

关键词：

D O I：

10.1021/ja990789h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first total synthesis of the marine macrolide miyakolide has been achieved, and its absolute stereochemistry has been determined. The carbon skeleton is assembled in a convergent fashion from three fragments via esterification, [3 + 2] dipolar cycloaddition, and aldol addition. The utility of beta-ketoimide aldol reactions in fragment coupling was demonstrated on fully elaborated intermediates. The coupled material was transformed into a 1,3,7-triketone-containing macrocycle that underwent a facile transannular aldol reaction followed by hemiketalization to form the oxydecalin ring system of the natural product. Deprotection afforded ent-miyakolide, which was produced in 6.8% overall yield and 29 linear steps.

引用

页码：6816 / 6826

页数：11