ⅠB和ⅡB族金属催化氢胺化反应的研究进展

Research progress in catalytic hydroamination of ⅠB and ⅡB metal catalysts

氢胺化反应是将氮氢键直接加成到碳碳不饱和键上的原子经济性反应,是一种合成胺类化合物的重要路径,在合成含氮化合物方面具有重要意义。本文首先介绍了氢胺化反应的机理,从活化胺类和活化不饱和烃类两个氢胺化反应机理的视角,详细阐述了ⅠB族中的Au、Ag、Cu和ⅡB族中的Zn 4种金属在氢胺化反应过程中活化底物的方式,并指出了ⅠB和ⅡB两族金属在氢胺化反应的热催化体系中存在的优缺点,在均相体系中反应温度较低,但操作步骤繁琐,催化剂不能循环利用,而在多相体系中可以实现催化剂的循环利用,但又面临着反应温度高的问题,因此开发温和条件下高效绿色的催化体系显得至关重要。此外,对光催化技术在氢胺化反应中的应用前景进行了展望,而非贵金属利用可见光在温和条件下实现高效催化氢胺化反应是未来的一个重要发展方向。

Hydroamination is an important and atom-economical route for the synthesis of amines through the direct addition of N—H bond to C—C multiple bond. This process is of great significance for the preparation of nitrogen-containing compounds. In this review,the mechanism of hydroamination was first presented. Four kinds of metal catalysts i.e, Au,Ag,Cu and Zn,which were typical representatives of group ⅠB and ⅡB,were discussed in detail in terms of their activation modes in the hydroamination of amines and unsaturated hydrocarbons. The advantages and disadvantages of these metal catalysts in the thermocatalytic system of hydroamination were analyzed. In homogeneous systems, the reaction temperature is low, but the operation were very complicated and the catalyst cannot be recycled, while the recycle of catalyst can be realized in heterogeneous systems, which in turn face the problem of high reaction temperature. Therefore, it is very important to develop high efficient green catalytic system operated under mild conditions. In addition, the potential of photocatalytic technology in hydroamination is prospected, and it is an important development direction for non-precious metals in the preparation of high efficient catalytic hydroamination under mild conditions by using visible light in the future.