借氢策略下醇胺化合成胺类化合物的多相催化剂研究进展

doi:10.6023/A26040126

摘要/Abstract

胺类化合物是医药、农药、精细化工等领域不可或缺的中间体与结构单元。基于借氢（Borrowing Hydrogen, BH）策略的醇与胺源（氨、伯胺、仲胺）的胺化反应,以理论上仅生成水为唯一副产物、近100%的原子经济性、反应条件温和、环境友好等优势,被公认为是胺类化合物绿色高效合成的主流路线之一。开发高活性、高选择性、高稳定性的多相催化剂是实现该反应工业化应用的核心关键。本文系统综述了借氢反应机制下醇胺化反应的多相催化体系研究进展。以脂肪醇和芳香醇等为典型反应底物,阐明了典型贵金属（Ru、Pd、Au）与非贵金属（Ni、Co、Cu、Mn）基催化剂在不同反应体系中的催化性能;深入讨论了金属-载体相互作用、载体表面酸碱性质、金属分散度、底物结构等关键因素对催化行为的调控规律;客观分析了各类催化体系的优势与现存瓶颈。最后,梳理了该领域当前面临的诸多挑战,并对未来的重点研究方向进行了总结与展望,为高性能醇胺化多相催化剂的理性设计提供参考。

关键词: 多相催化, 借氢策略, 醇胺化, 胺类化合物, 绿色合成

Amine compounds are indispensable intermediates and structural units in fields such as pharmaceuticals, pesticides, and fine chemicals. The amination reaction of alcohols and amine sources (ammonia, primary amines, secondary amines) based on the Borrowing Hydrogen (BH) strategy is recognized as one of the mainstream routes for the green and efficient synthesis of amine compounds due to its advantages, including the theoretical generation of water as the sole by-product, nearly 100% atom economy, mild reaction conditions, and environmental friendliness. The development of highly active, selective, and stable heterogeneous catalysts is crucial for the industrial application of this reaction. This paper systematically reviews the research progress of heterogeneous catalytic systems for alcohol amination reactions under the borrowing hydrogen reaction mechanism. Using typical reactants such as aliphatic and aromatic alcohols, it elucidates the catalytic performances of typical precious metal (Ru, Pd, Au) and non-precious metal (Ni, Co, Cu, Mn) based catalysts in different reaction systems. It further discusses the regulatory patterns of key factors such as metal-support interactions, the acid-base properties of the support surface, metal dispersion, and substrate structure on catalytic behavior. An objective analysis of the advantages and existing bottlenecks of various catalytic systems is also provided. Finally, the numerous challenges currently faced in this field are outlined, and future key research directions are summarized and anticipated, offering references for the rational design of high-performance heterogeneous catalysts for alcohol amination.

Key words: Heterogeneous catalysis, Borrowing hydrogen strategy, Alcohol amination, Amine compounds, Green synthesis.

引用此文

李平, 郑影, 刘少东, 苟焕其, 王鹏, 张博, 倪珺. 借氢策略下醇胺化合成胺类化合物的多相催化剂研究进展[J]. 化学学报, doi: 10.6023/A26040126.

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