用于石棉素的分子内狄尔斯-阿尔德策略：11-乙酰氧基-4-脱氧石棉素D和石棉素-12的对映选择性全合成

An intramolecular Diels-Alder strategy for the asbestinins: enantioselective total syntheses of 11-acetoxy-4-deoxyasbestinin D and asbestinin-12.

作者信息

Crimmins Michael T, Ellis J Michael

机构信息

Department of Chemistry, Venable and Kenan Laboratories of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.

出版信息

J Org Chem. 2008 Mar 7;73(5):1649-60. doi: 10.1021/jo0712695. Epub 2007 Oct 5.

DOI:10.1021/jo0712695

PMID:17918896

Abstract

The enantioselective total syntheses of 11-acetoxy-4-deoxyasbestinin D and asbestinin-12 have been completed. A glycolate aldol reaction provided a diene useful for ring-closing metathesis to form an oxonene, which was ultimately employed as a template to execute a highly stereoselective intramolecular Diels-Alder cycloaddition, forming the hydroisobenzofuran moiety. The absolute configuration of the asbestinin subclass was confirmed via these synthetic efforts.

摘要

11-乙酰氧基-4-脱氧石棉素D和石棉素-12的对映选择性全合成已完成。乙醇酸酯羟醛反应提供了一种可用于闭环复分解以形成氧杂环丁二烯的二烯，该二烯最终被用作模板来进行高度立体选择性的分子内狄尔斯-阿尔德环加成反应，形成氢化异苯并呋喃部分。通过这些合成工作确定了石棉素子类的绝对构型。