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Catalyst-free hierarchical reduction of CO2 with BH3N(C2H5)3 for selective N-methylation and N-formylation of amines
Journal of CO2 Utilization ( IF 7.7 ) Pub Date : 2021-05-28 , DOI: 10.1016/j.jcou.2021.101590
Qizhuang Zou , Yun Yi , Tianxiang Zhao , Fei Liu , Chao Kang , Xingbang Hu

We describe herein an efficient and catalyst-free methodology for N-formylation and N-methylation of various amines using BH3N(C2H5)3 as a reductant and CO2 as C1 source. This system is compatible with a wide range of substrates, such as aromatic secondary amines, aliphatic secondary amines, heterocyclic amines, and primary amines. The desired methylamines and formamides are obtained in excellent yields by changing the reaction solvent, temperature, and the amount of BH3N(C2H5)3. The optimum yields of methylamines and formamides are up to 99 %, which are comparable to the data using different catalysts. Moreover, it has been demonstrated by mechanistic research that CO2 was activated by inserting into B–H bonds of BH3N(C2H5)3 and formamide can be regarded as an intermediate species during the N-methylation formation.



中文翻译:

使用 BH 3 N(C 2 H 5 ) 3对CO 2进行无催化剂分级还原,用于胺的选择性N-甲基化和N-甲酰化

我们在本文中描述了使用 BH 3 N(C 2 H 5 ) 3作为还原剂和 CO 2作为 C1 源的各种胺的N-甲酰化和N-甲基化的有效且无催化剂的方法。该系统可与多种底物兼容,例如芳族仲胺,脂族仲胺,杂环胺和伯胺。通过改变反应溶剂、温度和 BH 3 N(C 2 H 5 ) 3的量,可以以极好的收率获得所需的甲胺和甲酰胺. 甲胺和甲酰胺的最佳产率高达 99%,与使用不同催化剂的数据相当。此外,机理研究表明,CO 2通过插入BH 3 N(C 2 H 5 ) 3 的B-H键而被活化,甲酰胺可被视为N-甲基化形成过程中的中间物质。

更新日期:2021-05-28
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