Weber Stefan, Veiros Luis F, Kirchner Karl
Institute of Applied Synthetic Chemistry Vienna University of Technology Getreidemarkt 9/163-AC A-1060 Wien Austria.
Centro de Química Estrutural, Instituto Superior Técnico Universidade de Lisboa Av. Rovisco Pais No. 1 1049-001 Lisboa Portugal.
Adv Synth Catal. 2019 Dec 3;361(23):5412-5420. doi: 10.1002/adsc.201901040. Epub 2019 Oct 28.
An efficient additive-free manganese-catalyzed hydrogenation of nitriles to primary amines with molecular hydrogen is described. The pre-catalyst, a well-defined bench-stable alkyl bisphosphine Mn(I) complex -[Mn(dpre)(CO)(CH)] (dpre=1,2-bis(di--propylphosphino)ethane), undergoes CO migratory insertion into the manganese-alkyl bond to form acyl complexes which upon hydrogenolysis yields the active coordinatively unsaturated Mn(I) hydride catalyst [Mn(dpre)(CO)(H)]. A range of aromatic and aliphatic nitriles were efficiently and selectively converted into primary amines in good to excellent yields. The hydrogenation of nitriles proceeds at 100 °C with a catalyst loading of 2 mol % and a hydrogen pressure of 50 bar. Mechanistic insights are provided by means of DFT calculations.
本文描述了一种高效的无添加剂锰催化腈与分子氢氢化生成伯胺的反应。预催化剂是一种定义明确、易于保存的烷基双膦锰（I）配合物-[Mn(dpre)(CO)(CH)]（dpre = 1,2-双（二-丙基膦基）乙烷），它会发生CO迁移插入到锰-烷基键中形成酰基配合物，该酰基配合物经氢解后生成活性配位不饱和的锰（I）氢化物催化剂[Mn(dpre)(CO)(H)]。一系列芳香族和脂肪族腈能以良好至优异的产率高效且选择性地转化为伯胺。腈的氢化反应在100°C下进行，催化剂负载量为2 mol%，氢气压力为50 bar。通过密度泛函理论（DFT）计算提供了机理见解。
