过渡金属催化硝基芳烃与末端炔烃交叉偶联构筑C(sp2)-C(sp)键的研究

构筑C(sp2)-C(sp)键是合成芳香炔烃及1,3-共轭烯炔等的最有效途径之一，在有机合成中占有重要地位。传统Sonogashira偶联构筑C(sp2)-C(sp)键时常存在卤代烃亲电试剂难制备较昂贵、多位点反应时偶联产物难分离、无法简捷高效制备环苯基多炔烃等缺陷。针对上述不足，本项目拟以硝基芳烃为亲电试剂，通过过渡金属催化其与末端炔烃交叉偶联来构筑C(sp2)-C(sp)键。拟设计建立和筛选Pd(II)/大位阻双烷基(双芳基)膦配体及Cu(I)/胺均相催化体系，建立催化剂结构与催化性能的构效关系，探索配体对Pd催化性能的作用机制及影响规律，揭示反应机理，认识反应的本质和规律，运用本交叉偶联反应合成环苯基多炔烃，改进其现有合成路线。本项目利用易制备且极性的硝基芳烃为亲电试剂将有望更简单经济有效地构筑C(sp2)-C(sp)键，并为炔烃衍生物的合成提供新方法和思路。

Construction of C(sp2)-C(sp), one of efficient methods for preparation of aromatic alkynes, 1,3-conjugated eneynes and so on, is important in organic synthesis. When we constructed C(sp2)-C(sp) by traditional Sonogashira coupling, we frequently experienced some inconvenience such as difficult to obtain expensive halohydrocarbon electrophilic synthon, difficult to separate multi-site coupling products and difficult to prepare cyclic phenyl polyynes efficiently. In order to solve the above inconvenience and to construct C(sp2)-C(sp) more efficiently, this project focuses on using nitroarenes as electrophiles, constructing C(sp2)-C(sp) through transition metal catalyed cross coupling with terminal acetylenes. The main contents of this project are designing, building and screening out Pd(II)/bulky dialkyl(diaryl) phosphine ligands and Cu(I)/amine homogeneous catalytic system, building structure-activity relationship of catalysts, studying the action mechanism and effect between ligands and Pd, revealing the reaction mechanism, recognizing the nature and law of this reaction, synthesizing cyclic phenyl polyynes by this coupling reaction to improve the present synthetic route. The implementation of this project will construct C(sp2)-C(sp) economically and efficiently using easy available and polar nitroarenes as electrophiles, and will provide new method and thought for preparation of acetylene derivatives.