阳离子型稀土硅胺基化合物促进的胺羰化/环化反应

项目名称： 阳离子型稀土硅胺基化合物促进的胺羰化/环化反应

项目编号： No.21502070

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 洪建权

作者单位： 江南大学

项目金额： 21万元

中文摘要： 胺羰基化反应是一种应用范围广的合成大宗基础化工原料及高附加值精细化工产品和天然产物的重要方法，但是，迄今催化这类反应所使用的催化剂主要是后过渡金属络合物。本项目拟通过稀土金属有机催化剂的设计合成，开拓性研究稀土金属对不饱和胺的分子内胺羰化/环化反应的催化作用。具体研究内容包括阳离子型单茂稀土硅胺基化合物的设计合成，稀土金属络合物与CO的基元反应，稀土催化邻位功能取代芳香胺与CO的胺羰化/环化反应，稀土催化各种不饱和脂肪胺与CO的胺羰化/环化反应等。拟通过反应底物的设计和稀土金属配位环境的调控，实现不稳定稀土酰基络合物与分子内其它不饱和官能团的快速加成，建立稀土金属活化CO的新模式，发展调控稀土配合物与CO反应选择性的新策略，为开发稀土在有机合成中的应用探明新方向。

中文关键词： 稀土化合物；胺羰化/环化；C1砌块；催化活性；内酰胺

英文摘要： Aminocarbonylation of organic substrates is among the most important and wildly applied method for synthesis of commodity basic chemicals, high value-added fine chemicals and natural products. However, catalysts employed in these reactions are mainly late transition-metal complexes to date. We propose to design and synthesize novel organolanthanide catalysts, and to develop a pioneering work on rare-earth metal-catalyzed intramolecular aminocarbonylation/cyclization of unsaturated amines. The primary research covers designed synthesis of cationic rare-earth metal silylamide complexes, elementary reaction between rare-earth metal complexes and CO, aminocarbonylation/ cyclization of ortho-functionalized aromatic amines and CO promoted by rare-earth metals and rare-earth metal-catalyzed aminocarbonylation/ cyclization of unsaturated aliphatic amines and CO, and so on. With appropriate design of unsaturated organic substrates and regulating the coordinated surroundings around the rare-earth metal, we propose to achieve a fast intramolecular addition of acyl group to other unsaturated functional group in acyl rare-earth metal intermediate. In general, we are going to establish a novel CO activation pattern mediated by rare-earth complexes, to develop new strategy for controlling the reaction selectivity of rare-earth complexes and CO, and to open up new application of rare-earth metals in organic synthesis.

英文关键词： rare-earth metal compound;aminocarbonylation/cyclization;C1 building block;catalytic activity;lactam