对映选择性有机催化还原胺化反应。

Enantioselective organocatalytic reductive amination.

作者信息

Storer R Ian, Carrera Diane E, Ni Yike, MacMillan David W C

机构信息

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

出版信息

J Am Chem Soc. 2006 Jan 11;128(1):84-6. doi: 10.1021/ja057222n.

DOI:10.1021/ja057222n

PMID:16390133

Abstract

The first enantioselective organocatalytic reductive amination reaction has been accomplished. The development of a new chiral phosphoric acid catalyst has provided a convenient strategy for the enantioselective construction of protected primary amines and provided a highly stereoselective method for the reductive amination of heterocyclic amines. A diverse spectrum of ketone and amine substrates can be accommodated in high yield and excellent enantioselectivity. This new protocol realizes a key benefit of reductive amination versus imine reduction, in that ketimines derived from alkyl-alkyl ketones are unstable to isolation, a fundamental limitation that is comprehensively bypassed using this direct organocatalytic reductive amination.

摘要

首次实现了对映选择性有机催化还原胺化反应。新型手性磷酸催化剂的开发为对映选择性构建受保护的伯胺提供了一种便捷策略，并为杂环胺的还原胺化提供了一种高度立体选择性的方法。多种酮和胺底物能够以高产率和优异的对映选择性得到应用。该新方法实现了还原胺化相对于亚胺还原的一个关键优势，即源自烷基 - 烷基酮的酮亚胺不稳定，难以分离，而使用这种直接的有机催化还原胺化可全面绕过这一基本限制。