| 邱昊,林延欣,单斌,崔兆杰,王新波.化学通报,2023,86(7):853-862. |
| 氰基衍生化制备胺的研究进展 |
| Advances in the Preparation of Amines by Nitrile Derivatization |
| 投稿时间：2022-11-28 修订日期：2023-01-02 |
| DOI： |
| 中文关键词: 氰基 胺 催化 制备 衍生化 加氢 |
| 英文关键词:nitriles amines catalysis preparation derivatization hydrogenation |
| 基金项目:国家自然科学基金项目(22078174,21808118)、大连理工大学精细化工国家重点实验室开放课题项目(KF2114)、广东省基础与应用基础研究基金项目(2022A1515011856)和深圳市科技计划项目(JCYJ20220530141205012)资助 |
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| 中文摘要: |
| 胺是有机分子中最常见且重要的结构之一,广泛存在于天然产物分子、药物、染料、塑料等的分子结构中,开发合成胺的有效方法在化学工业中具有很高的需求但仍充满挑战。在诸多已知有机胺的合成方法中,以氰基为前体还原衍生化制备胺被认为是一条原子经济且绿色可行的方案。然而,氰基中存在稳定的碳氮三重键,还原过程涉及较多中间体,而部分中间体活性比氰基更高,因此反应受还原剂、催化剂、反应条件的影响很大,由氰基选择性制备目标胺结构仍充满挑战。本文从氰基的基本电子结构与反应活性出发,综述了近年来以氰基为原料的官能团胺基化反应,对部分重要反应的催化剂和反应机理做了简要讨论,为设计氰基制胺催化剂和应用工艺提供了新的视角。 |
| 英文摘要: |
| Amines, including primary, secondary and tertiary amines, are one of the most common and useful structures in organic molecules. They are widely found in the molecular structures of natural products, drugs, dyes, plastics and so on. The development of effective methods for synthesizing amines has a high demand in the chemical industry, but it is still full of challenges. Among many known synthetic methods of organic amines, such as hydroamination of olefins, nucleophilic substitution, metal catalyzed C-N coupling, etc., nitrile group reductive derivatization is considered to be a relatively green and feasible scheme. However, the carbon nitrogen triple bonds in the cyano group are high in energy, and many intermediates are involved in the reduction process. In addition, some intermediates are even more active than the cyano group. Therefore, the reaction is greatly affected by reducing agents, catalysts and reaction conditions. Starting from the basic electronic structure and reaction activity of cyano group, this paper summarizes the functional group amination reactions using nitriles as raw materials in recent years. The catalysts design and reaction mechanisms of some important reactions are discussed briefly, with the aim to provide a new perspective for the design of catalysts and application processes of amines. |
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