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离子液体接枝的有机催化剂在有机合成中的反应研究
Studies on the Application of Ionic Liquid Grafted Organic Catalyst in Organic Synthesis
【作者】 杨尚东;
【导师】 梁永民;
【作者基本信息】 兰州大学 , 有机化学, 2006, 博士
【摘要】 本论文主要研究了以脯氨酸为起始原料合成咪唑类离子液体接枝的有机催化剂并应用于有机催化反应中的研究。本文共包括三个部分: 一、离子液体在有机催化反应中的应用概述(综述) 室温下的离子液体作为一种绿色、环保的,可替代传统有机溶剂的新型溶剂受到了各国化学家们的极大关注,已经在有机合成化学中获得了广泛的应用。在这章我们主要概述了离子液体的发展、合成以及作为反应介质在有机合成中的应用。另外,特别介绍了一些具有特殊功能的离子液体的合成及其在有机催化反应中的应用。 二、离子液体接枝的有机小分子催化的反应研究 这章主要介绍了功能性离子液体在有机催化反应中的应用。在这里,我们小组报道了用脯氨酸为原料合成了一种双官能团的离子液体接枝的新型有机催化剂并应用于Aldol缩合反应,它和脯氨酸具有相似的催化作用,可以有效地促进反应的进行。同时也具有离子液体的特殊功能,为催化剂的回收和再利用提出了一种新的方式。 三、离子液体接枝的手性配体参与的不对称催化还原反应的研究 随着Corey小组把脯胺醇成功地用于硼烷的不对称还原反应以后,合成新的手性氨基醇配体并研究其在手性噁唑硼烷催化的不对称还原反应中的效应成为一个新的研究热点。在这里我们报道了一种离子液体接枝的磺酰胺手性配体以及在前手性酮的不对称还原反应中的应用,获得了较好的对映纯过量,实现了手性配体的回收和重复使用。
【Abstract】 This thesis introduces the studies on two types of ionic liquid grafted organic catalysts, in which proline were used as starting materials, and applications to the catalysis of organic reactions. This thesis is mainly divided into the following three parts as follows:1. Application of ionic liquids in catalyzed organic reactions (review)Ionic liquids, as one kind of new environmental friend solvent to replace of traditional organic solvents, attract more attention from chemists. They have been applied to many organic reactions. This review summarizes the history of ionic liquid chemistry and the application for reaction medium. In particular, it introduces the synthesis of task-specific ionic liquids and the application to the catalysis of organic reactions.2. Studies on ionic liquid grafted small organic molecule catalyzed reactions This chapter mainly introduces the organocatalysts application in ionic liquids. Wereport the synthesis of an alkyl imidazolium salt supported pyrrolidine amide organocatalyst L-1 and its use and recycling in Aldol condensation reaction. It was prepared based on L-proline and this bifunctional molecule having a basic pyrrolidine and a significantly acidic amide moiety could function the same ways as L-proline does for promoting reactions, synchronously having speciality of ionic liquid could easy to separated and recycled.3. Studies on ionic liquid grafted chiral ligand catalyzed asymmetric reduction reactionsSince the Corey group reported the CBS catalyzed borane asymmetric reduction, much amino alcohols were synthesis and application in research of chiral oxazaboro-lidines catalyzed reduction. In this chapter, we report the synthesis of an alkyl imidazo lium salt supported chiral sulfonamide ligand and its use and recycling in enantiosel-ective reduction of prochiral ketones to optically active secondary alcohols.