不对称串联反应中化学选择性的控制：手性含非紧邻立体中心的胺的直接合成。
Control of chemoselectivity in asymmetric tandem reactions: Direct synthesis of chiral amines bearing nonadjacent stereocenters.
机构信息
Department of Chemistry, Brandeis University, Waltham, MA 02454-9110.
Department of Chemistry, Brandeis University, Waltham, MA 02454-9110
出版信息
Proc Natl Acad Sci U S A. 2018 Feb 20;115(8):1730-1735. doi: 10.1073/pnas.1718474115. Epub 2018 Feb 5.
Abstract
This paper describes the mechanistic insight-guided development of a catalyst system, employing a phenolic proton donor catalyst in addition to a cinchonium-derived phase-transfer catalyst, to control the chemoselectivity of two distinct intermediates, thereby enabling the desired asymmetric tandem conjugate addition-protonation pathway to dominate over a number of side-reaction pathways to provide a synthetic approach for the direct generation of optically active amines bearing two nonadjacent stereocenters.
摘要
本文描述了一种基于机理洞察的催化剂体系的开发，该体系采用酚类质子供体催化剂和源于 cinchonium 的相转移催化剂来控制两种不同中间体的化学选择性，从而使所需的不对称串联加成-质子化反应途径占主导地位，而不是许多副反应途径，为直接生成具有两个非相邻手性中心的光学活性胺提供了一种合成方法。
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