基于Catellani反应合成轴手性和平面手性化合物的研究

项目名称： 基于Catellani反应合成轴手性和平面手性化合物的研究

项目编号： No.21472179

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 顾振华

作者单位： 中国科学技术大学

项目金额： 95万元

中文摘要： 化合物的手性可分为中心手性、轴手性、平面手性和螺手性等，相对于中心手性而言，后三者的研究相对较少。本研究拟通过以降冰片烯为媒介的钯催化的Catellani反应来研究合成轴手性和平面手性化合物。轴手性可以通过邻位引入取代基而使芳基-芳基轴的自由旋转受到限制而产生，平面手性化合物可以通过化合物的平面引入不同的取代基而使平面失去对称性而产生。本研究计划分三部分，1）钯催化的Catellani反应先引入邻位取代基，然后构建芳基-芳基结构，其轴手性产生于后面的芳基-芳基的形成一步；2）芳基-芳基母核已经构建好的基础上，再在邻位引入取代基，这里轴手性的控制在于邻位官能化一步；3）在平面手性化合物合成过程中，通过手性配体， 如手性膦配体等的使用使邻位官能化形成五元碳钯中间体时优先形成某一平面手性环钯化合物，然后通过动力学控制反应的过程，从而构建平面手性化合物。

中文关键词： 催化；钯；降冰片烯；轴手性；平面轴手性

英文摘要： Chiralities in organic compounds are including central chirality, axial chirality, planar chirality and helical chirality etc. Compare to central chirality, relatively less attentions have been paid to the catalytic synthesis of compounds that containing other chiralities. This research proposal are going to study the constrution of axial and planar chiralities by the use of palladium-catalyzed norbornene-mediated Catellani reaction. It is possible that generate axial chirality by introducing an ortho group to inhibit the free rotation of the biaryl moiety. The planar chirality could be constructed by introdcing two different groups onto the plane of a pre-planar chiral molecules. This research plan was divided into three parts: 1) introducing an ortho-group of aryl halides followed aryl-aryl coupling by palladium-catalyzed Catellani reaction. The axial chirality was constructed at the step that the formation of aryl-aryl bonds. 2) Introducing an ortho-group to biaryl compounds to prohibit the free rotation of the aryl rings, where the axial chirality was controlled at the step of ortho-functionalization. 3) In the synthesis of planar chiral compounds, the chiral ligand for palladium, such as chiral phosphine might be able to descriminate two ortho C(aryl)-H bond. Thus, the reaction would like to form one planar chiral cyclopalldium species over the other, and as a result the reaction would give planar chiral compound by kinetic control.

英文关键词： catalysis;palladium;norbornene;axial chirality;planar chirality