A Practical and Benign Synthesis of Primary Amines through Ruthenium‐Catalyzed Reduction of Nitriles

Abstract

The catalytic hydrogenation of nitriles represents an atom-economic and valuable route to amines. In the present study, the ruthenium-catalyzed hydrogenation of various organic nitriles to give primary amines has been examined in detail. Straightforward ruthenium complexes modified by cheap and widely available triphenylphosphine allow for the efficient and general reduction of various aryl, alkyl, and heterocyclic nitriles. By using a practical in situ catalyst composed of [Ru(cod)(methylallyl(2))] and PPh(3), excellent yields and chemoselectivity were achieved. Moreover, the catalyst system displays broad functional group tolerance.

Tuning the selectivity of ruthenium nanoscale catalysts with functionalised ionic liquids: Hydrogenation of nitriles

“…Moreover, it is well known that the hydrogenation of PhCN to benzylamine is catalysed by molecular complexes [22][23][24]. In the case of metal surfaces [20,21,25] the activated amine -benzylamine -is rapidly transformed into the benzylidene benzylamine via aminolysis and coupling although we were unable to detect neither benzylamine nor benzylimine by ESI-MS and NMR experiments.…”

“…In the case of metal surfaces [20,21,25] the activated amine -benzylamine -is rapidly transformed into the benzylidene benzylamine via aminolysis and coupling although we were unable to detect neither benzylamine nor benzylimine by ESI-MS and NMR experiments. As already pointed out benzylamine undergoes exclusively aminolysis with solid catalysts, in contrast molecular catalysts give benzylamine as main product [22][23][24].…”

Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

“…Takemoto et al [58] and Li et al [59] reported examples of homogeneous hydrogenation of nitriles into primary amines when alkoxide were added to ruthenium catalyst. Das et al [60] and Enthaler et al [61,62] also showed that addition of t BuOK and phosphine to simple ruthenium complex led to the fast hydrogenation of various nitriles and by replacing the phosphine ligand by a N-heterocyclic carbene, milder conditions could be operating [63].…”

Surface Properties of Ni/MgO Catalysts for the Hydrogenation of Lauronitrile

“…Catalytic hydrogenation of nitriles is an important process for the preparation of diverse amines industrially. For example, hexamethylenediamine, stearylamine, dodecylamine, benzylamine, and xylyenediamine are usually prepared by the hydrogenation of corresponding adiponitrile, stearonitrile, lauronitrile, benzonitrile, and 1,4-dicyanobenzene [1][2][3][4][5][6][7][8][9][10]. These reactions are usually catalyzed in liquid phase at elevated temperatures and pressures.…”