Department of Chemistry, Northeastern University, Shenyang, 110819, P. R. China.
School of Materials Science and Engineering, Northeastern University, Shenyang, 110819, P. R. China.
Chempluschem. 2020 Aug;85(8):1783-1788. doi: 10.1002/cplu.202000028.
Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by-products. Herein we report a magnetic quaternary-component Pt-CuFe/Fe O nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d-band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h . A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.
腈的氢化是合成对称仲胺的一种有效且环保的方法，但通常会产生胺、亚胺和氢解副产物的混合物。本文报道了一种磁性四组分 Pt-CuFe/Fe O 纳米催化剂体系，用于以氨硼烷为氢供体选择性合成对称仲胺。低 Pt 负载量（0.456wt%）的催化剂是活性的来源，Cu 到 Fe 的 d 带电子转移增强了选择性。这种协同效应导致苯甲腈在温和的反应条件下转化为二苄胺，转化率高达 99%，选择性接近 100%（高达 96%），然而，反应 TOF 高达 1409.9h 。各种腈都适合合成对称仲胺。更重要的是，根本没有检测到不需要的氢解副产物，尤其是甲苯。此外，该催化剂可通过磁性回收，可重复使用五次以上。
