手性过渡金属配合物催化下非官能化烯烃的不对称卤胺化反应

项目名称： 手性过渡金属配合物催化下非官能化烯烃的不对称卤胺化反应

项目编号： No.21272121

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 李月明

作者单位： 南开大学

项目金额： 80万元

中文摘要： 非活化碳碳双键的官能化是有机合成中一类重要反应。它以非官能化烯烃为原料，通过碳碳双键上的各种反应，将简单烯烃转化成重要的有机合成中间体。邻卤胺化合物是有机合成及药物合成的重要中间体，使用氨基和卤素同时对碳碳双键官能化是制备这类化合物最直接的手段之一。目前这类反应大多集中在alpha,beta-不饱和化合物等反应活性较高的底物，而对非官能化烯烃的研究则相对较少。 本研究基于我们对非官能化烯烃反应的理解，以4-戊烯胺等非官能化烯烃为模型底物、手性过渡金属配合物为催化剂进行非官能化烯烃的不对称卤胺化反应。通过改变催化剂的Lewis酸性及配体的空间电子因素，研究在氨基等配位性基团存在下碳碳双键的选择性活化，研究过渡金属d电子结构对其催化能力的影响，以及不同条件下反应中间体金属-碳键的断裂方式，扩展非活化烯烃的官能化反应，发展重要手性含氮化合物的不对称合成新方法。

中文关键词： 非官能化烯烃；卤胺化；噁唑啉；吡咯烷；硼胺化

英文摘要： Functionalization of un-activated C=C double bonds is one of the most important reactions in organic synthesis. In the presence of a suitable catalyst, the reaction converts unfunctionalized olefins to important organic and pharmaceutical intermediates through (di)hydroxylation, (di)amination, aminohydroxylyation or epoxidation of C=C double bonds. Vincinal haloamine compounds are important intermediates for organic synthesis and drug synthesis, and a variety of nitrogen-containing compounds can also be prepared from these intermediates. In addition, they also appear as important subunits in some natural products and antitumor agents. Direct functionalization of C=C double bond with halogen and amino group is the most straightforward method for the synthesis of this type of important compounds. Most of the current studies focused on alpha, beta-unsaturated and related substrates, and only a few works were reported for haloamination of unfunctionalized olefins. These reported methods utilized palladium-copper or palladium-copper-carbonate multi-metal systems, and relatively harsh conditions were normally required. Very recently, we found that several 4-penten-1-amine substrates were able to undergo chloroamination in the presence of CuCl2. The reactions were easy to perform, and all the operations could be carri

英文关键词： unfunctionalized olefins；haloamination；oxazoline；pyrrolidine；aminoboration