Old Concepts, New Application – Additive‐Free Hydrogenation of Nitriles Catalyzed by an Air Stable Alkyl Mn(I) Complex. Issue 23 (28th October 2019)

• Record Type: Journal Article
• Authors: Weber, Stefan; Veiros, Luis F.; Kirchner, Karl
• Is Part Of: Advanced synthesis & catalysis. Volume 361:Issue 23(2019)
• Page Start: 5412
• Page End: 5420
• Publication Date: 2019-10-28
• Subjects: manganese -- alkyl complexes -- hydrogenation -- nitriles -- migratory insertion; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201901040
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: 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 fac ‐[Mn(dpre)(CO)3 (CH3 )] (dpre=1, 2‐bis(di‐ n ‐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)2 (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. Abstract :