Stereoselective Construction of Adjacent Quaternary Chiral Centers by the Ireland-Claisen Rearrangement: Stereoselection with Esters of Cyclic Alcohols
Stereoselective Construction of Adjacent Quaternary Chiral Centers by the Ireland-Claisen Rearrangement: Stereoselection with Esters of Cyclic Alcohols
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DOI：
10.1055/s-0029-1219965
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发表时间：
2010-07-01
期刊：
影响因子：
2
通讯作者：
Zakarian, Armen
中科院分区：
文献类型：
--
作者：
Gu, Zhenhua;Herrmann, Aaron T.;Zakarian, Armen
本工作描述了一个研究的爱尔兰克莱森重排的α，α-二取代烯醇衍生自环状醇酯。高立体选择性的烯醇化反应通常可以通过匹配酯和碱的手性而使用N-苄基Koga型碱来实现。[3，3]-σ转移重排反应以良好的产率和中等的非对映选择性进行，形成两个相邻的四元立体中心，并通常通过椅状过渡态进行。
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.