Stereoselective Construction of Adjacent Quaternary Chiral Centers by the Ireland-Claisen Rearrangement: Stereoselection with Esters of Cyclic Alcohols

被引：36

作者：

Gu, Zhenhua ^{[1
]}

Herrmann, Aaron T. ^{[1
]}

Stivala, Craig E. ^{[1
]}

Zakarian, Armen ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

来源：

SYNLETT | 2010年 / 11期

基金：

美国国家科学基金会;

关键词：

diastereoselectivity; rearrangement; esters; sigmatropic; chirality; stereoselective synthesis; CARBOXYLIC-ACID DERIVATIVES; ASYMMETRIC ALKYLATION; FUNCTIONAL-GROUPS; PINNATOXINS; TRANSITION; FRAGMENT; SOLVENT;

D O I：

10.1055/s-0029-1219965

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

This work describes a study of the Ireland-Claisen rearrangement of alpha,alpha-disubstituted enolates derived from esters of cyclic alcohols. Highly stereoselective enolizaitions could be generally achieved using N-benzyl Koga-type bases by matching chirality of the ester and the base. The [3,3]-sigmatropic rearrangement took place in good yields and moderate diastereoselectivity forming two adjacent quaternary stereogenic centers, and generally proceeding through a chairlike transition state.

引用

页码：1717 / 1722

页数：6

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