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Efficient and selective approach to biomass-based amine by reductive amination of furfural using Ru catalyst
Applied Catalysis B: Environment and Energy ( IF 20.2 ) Pub Date : 2022-03-02 , DOI: 10.1016/j.apcatb.2022.121262
Hongtao Zou 1 , Jinzhu Chen 1
Affiliation  

Reductive amination of furfural (1a) to furfurylamine (2a) was developed as a powerful and practical approach to biomass-based amine. Herein, Ru catalyst (Ru/BNC) supported on boron/nitrogen co-doped carbon (BNC) was reported for the reductive amination with hydrous hydrazine (N2H4·H2O) as a nitrogen source and hydrazone as intermediate. Our mechanism investigation suggested rich Frustrated Lewis acid−base pairs (FLPs) on the BNC surface synergistically enhanced the activity of Ru catalyst. Moreover, quick formation rate of hydrazone intermediate and its moderate reactivity significantly improved 2a selectivity. Under optimal conditions, Ru/BNC catalyst can highly efficiently and selectively promote 1a/N2H4-to-2a transformation with 2a yield exceeding 99%. Moreover, the role of nitrogen sources such as N2H4, NH3 and hydroxylamine on the 2a selectivity was systematically investigated. Additionally, the developed Ru/BNC−N2H4 system was applicable to a wide range of aldehydes to give the desired primary amines in excellent to good yields (85–99%) in the reductive amination reaction.



中文翻译:

使用Ru催化剂通过糠醛还原胺化制备生物质胺的高效选择性方法

糠醛 ( 1a ) 还原胺化为糠胺 ( 2a ) 被开发为一种强大且实用的生物质胺基方法。在此,报道了负载在硼/氮共掺杂碳(BNC)上的Ru催化剂(Ru/BNC)用于以水合肼(N 2 H 4 ·H 2 O)为氮源,腙为中间体的还原胺化反应。我们的机理研究表明,BNC 表面上丰富的受挫路易斯酸碱对 (FLP) 协同增强了 Ru 催化剂的活性。此外,腙中间体的快速形成速率及其中等反应性显着提高2a选择性。在最佳条件下,Ru/BNC催化剂可以高效、选择性地促进1a /N 2 H 4向2a转化,2a产率超过99%。此外,系统研究了N 2 H 4、NH 3和羟胺等氮源对2a选择性的影响。此外,所开发的 Ru/BNC-N 2 H 4体系适用于多种醛类,在还原胺化反应中以优异的产率(85-99%)得到所需的伯胺。

更新日期:2022-03-02
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