The catalytic hydroamination reaction of ethylene with diethylamine in the presence of lithium diethylamide has been reinvestigated to improve catalyst productivity. Various tertiary amines were synthesized and screened as ligands for the target reaction. Applying N,N,N',N'-tetramethylethylenediamine (TMEDA) or N,N,N,N '',N ''-pentamethyldiethylentriamine (PMDTA) the rate of the reaction is increased, but also ligand degradation is observed. Using optimized parameters excellent yield (92%) and conversion (99%) were achieved under mild conditions. At higher temperature base-catalyzed hydroamination of higher olefins is also possible. (c) 2005 Elsevier B.V. All rights reserved.