Attempts To Improve the Overall Stereoselectivity of the Ireland-Claisen Rearrangement

被引：28

作者：

Chen, Chi-Li ^{[1
]}

Namba, Kosuke ^{[1
]}

Kishi, Yoshito ^{[1
]}

机构：

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

来源：

ORGANIC LETTERS | 2009年 / 11卷 / 02期

基金：

美国国家卫生研究院;

关键词：

ANTITUMOR POLYETHER MACROLIDE; SPONGE LISSODENDORYX SP; HALICHONDRIN-B; MARINE SPONGE; NORHALICHONDRIN-B; D-GLUCOSE; RING; CONSTRUCTION; INTERMEDIATE; SEGMENT;

D O I：

10.1021/ol8027225

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

With focus on the steric effects present in the transition states for the [3,3]-sigmatropic rearrangement, the substrate 5 has been designed to improve the overall stereoselectivity of the Ireland-Claisen rearrangement. Experimentally, it has been found that (1) only Z-6 rearranges to 7 at 80 degrees C and (2) E-6 isomerizes to Z-6 at 80 degrees C, thereby allowing the transformation of 5 into 7 in an almost quantitative yield. To illustrate the usefulness of this approach, two additional examples are given.

引用

页码：409 / 412

页数：4

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