The reaction of buta-1,3-diene with morpholine and di-n-propylamine in the presence of NiCl2–Ph3P–NaBH4, CoCI2–Ph3P–NaBH4–AI(OPri)3, and IrCI3 has been shown to yield two isomeric 2 : 1 and 1 : 1 adducts with the former predominating. In the presence of RhCI3 and CoCI2–Ph3P–NaBH4 mainly 1 : 1 adducts were obtained. Lower conversions were found with morpholine and the nickel-containing system when the ligands di-isopropoxyphenylphosphine, tri-(o-tolyl) phosphite, and tri-(o-biphenylyl) phosphite were employed although exclusive 2 : 1 adduct formation was found with the last ligand. The addition of triphenyl-phosphine and -arsine to the RhCI3 catalyst also favoured formation of the 2 : 1 adduct and the catalytic activity of IrCI3 was markedly enhanced by small amounts of hydrochloric acid. Some reactions of diethylamine, pyrrolidine, and aniline have been studied. Reaction of benzyl methyl ketone and diethyl malonate with buta-1,3-diene catalysed by NiCl2–Ph3P–NaBH4 yields mainly the 2 : 1 adducts. With the system CoCI2-Ph3P-NaBH4, prior formation of the sodium salt of diethyl malonate was required for reaction with buta-1,3-diene.