Hydroaminations of methyl methacrylate with pyrrolidine and piperidine were found to proceed without a catalyst under mild conditions. Hydroamination with morpholine catalyzed by cationic palladium diphosphinoazine complexes was studied at temperatures 20-80 degrees C with catalyst loadings 0.1-1.05 mol%. Yields up to 91% were achieved and the promotion of the catalysis by triflic acid or its silver salt established. The influence of the phosphorus substitution in the diphosphinoazine on the catalytic activity was also observed. (c) 2006 Elsevier B.V. All rights reserved.