IB和IIB族金属催化氢胺化反应的研究进展

doi:10.16085/j.issn.1000-6613.2018-0897

化工进展 ›› 2019, Vol. 38 ›› Issue (04): 1730-1738.DOI: 10.16085/j.issn.1000-6613.2018-0897

IB和IIB族金属催化氢胺化反应的研究进展

刘沛¹(),谷献模²,孔鹏^1,²,李忠¹(),郑占丰²()

1. 太原理工大学煤科学与技术教育部和山西省重点实验室，山西太原 030024
2. 中国科学院山西煤炭化学研究所煤转化国家重点实验室，山西太原 030001

收稿日期:2018-05-02 修回日期:2018-06-20 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 李忠,郑占丰
作者简介:<named-content content-type="corresp-name">刘沛</named-content>（1992—），男，硕士研究生，研究方向为光催化绿色合成。E-mail：<email>Liu_P1992@126.com</email>。|李忠，博士，教授，博士生导师，研究方向为多相催化。E-mail：<email>lizhong@tyut.edu.cn</email>|郑占丰，博士，研究员，博士生导师，研究方向为光催化绿色合成。E-mail：<email>zfzheng@sxicc.ac.cn</email>
基金资助:
国家自然科学基金(51401233，21503258)

Research progress in catalytic hydroamination of IB and IIB metal catalysts

Pei LIU¹(),Xianmo GU²,Peng KONG^1,²,Zhong LI¹(),Zhanfeng ZHENG²()

1. Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
2. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China

Received:2018-05-02 Revised:2018-06-20 Online:2019-04-05 Published:2019-04-05
Contact: Zhong LI,Zhanfeng ZHENG

摘要/Abstract

摘要：

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。

关键词: IB族金属, IIB族金属, 催化, 活化, 氢胺化反应

Abstract:

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.

Key words: IB metal, IIB metal, catalysis, activation, hydroamination

中图分类号:

O622.6

刘沛, 谷献模, 孔鹏, 李忠, 郑占丰. IB和IIB族金属催化氢胺化反应的研究进展[J]. 化工进展, 2019, 38(04): 1730-1738.

Pei LIU, Xianmo GU, Peng KONG, Zhong LI, Zhanfeng ZHENG. Research progress in catalytic hydroamination of IB and IIB metal catalysts[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1730-1738.

图/表 11

图1 不饱和烃与胺的氢胺化反应

图2 金属催化氢胺化反应的两种机理

图3 负载型金纳米颗粒光催化炔烃氢胺化反应的机理[18]

图4 铜活化胺驱动炔烃氢胺化反应的机理[23]

图5 Cu-NCN催化炔烃的氢胺化反应[23]

图6 锌活化胺驱动氢胺化反应的机理[25]

图7 金活化炔烃氢胺化反应的机理[33]

图8 AgNO3催化末端炔烃与胺的氢胺化反应[40]

图9 Ag/CNT催化内炔烃与胺的氢胺化反应[41]

图10 锌活化炔烃氢胺化反应的机理[46]

图11 DMC催化炔烃与胺的分子间氢胺化反应[47]

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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

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