Ruthenium/Imidazolylphosphine Catalysis: Hydrogenation of Aliphatic and Aromatic Nitriles to Form Amines

• Published in: Chemistry : a European journal Vol. 20; no. 15; pp. 4227 - 4231
• Main Authors: Werkmeister, Svenja, Junge, Kathrin, Wendt, Bianca, Spannenberg, Anke, Jiao, Haijun, Bornschein, Christoph, Beller, Matthias
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 07.04.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Aliphatic compounds; amine; Amines; Amines - chemistry; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Coordination Complexes - chemistry; Crystal structure; Crystallography, X-Ray; Hydrogenation; Imidazoles - chemistry; Ligands; Molecular Conformation; N ligands; nitrile; Nitriles; Nitriles - chemistry; P,N ligands; Phosphines - chemistry; Physical Sciences; Ruthenium; Ruthenium - chemistry; Science & Technology; SELECTIVE HYDROAMINOMETHYLATION; CARBOXYLIC-ACID ESTERS; COMPLEXES; HYDROAMINATION; hydrogenation; P; ruthenium; ALKENES; N ligands; ATOMS LI; REDUCTION; LIGANDS; ENANTIOSELECTIVE HYDROGENATION; nitrile; amine; GAUSSIAN-BASIS SETS; P,N ligands
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201303989

A convenient and efficient catalyst system for the hydrogenation of aliphatic nitriles towards the corresponding primary amines in high to excellent yields is presented. In addition, aromatic nitriles are reduced smoothly, too. The use of low catalyst loadings and molecular hydrogen make this protocol an attractive methodology. It's not complicated: A general and easy homogeneous catalyst system based on [Ru(cod)(methylallyl)2] and a cyclohexyl‐substituted imidazolylphosphine ligand for selective hydrogenation of aliphatic nitriles is presented. In addition, by using an isopropyl‐substituted imidazolylphosphine ligand, selected aromatic nitriles were reduced with excellent yields towards the primary amine. Furthermore, two new crystal structures give an insight of possible pre‐catalysts.