对映选择性有机催化分子内狄尔斯-阿尔德反应。茄尼酮D的不对称合成。

Enantioselective organocatalytic intramolecular Diels-Alder reactions. The asymmetric synthesis of solanapyrone D.

作者信息

Wilson Rebecca M, Jen Wendy S, Macmillan David W C

机构信息

Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.

出版信息

J Am Chem Soc. 2005 Aug 24;127(33):11616-7. doi: 10.1021/ja054008q.

DOI:10.1021/ja054008q

PMID:16104734

Abstract

The first direct enantioselective organocatalytic intramolecular Diels-Alder reaction has been accomplished. The use of iminium catalysis has provided a new catalytic strategy for the enantioselective [4 + 2] cycloisomerization of a wide variety of tethered diene-enal systems. The use of imidazolidinones 1 and 2 as the asymmetric catalysts has been found to mediate the enantioselective construction of [4.4.0] and [4.3.0] ring systems. Application of this methodology to the highly efficient asymmetric synthesis of the marine metabolite solanpyrone D has also been accomplished. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. Importantly, this technology has been utilized to execute the first enantioselective, catalytic Type II IMDA reaction.

摘要

首次实现了直接对映选择性有机催化分子内狄尔斯-阿尔德反应。亚胺催化的应用为各种连接的二烯-烯醛体系的对映选择性[4 + 2]环异构化提供了一种新的催化策略。已发现使用咪唑烷酮1和2作为不对称催化剂可介导[4.4.0]和[4.3.0]环体系的对映选择性构建。该方法在海洋代谢产物茄尼酮D的高效不对称合成中的应用也已完成。在这种新的有机催化转化中也可以容纳多种醛底物。重要的是，该技术已被用于进行首例对映选择性催化II型IMDA反应。