A series of late transition metals have been found to catalyse the intramolecular addition of amines to alkynes. 6-Amino-1-hexyne is catalytically converted to 2-methyl-1,2-dehydropiperidine employing group 9, 10 or 11 metal complexes. The best results were obtained with the palladium and rhodium complexes Pd(CH 3 CN) 4 (BF 4 ) 2 and Rh(COD)(DIPAMP)BF 4 . All catalytically active complexes have d 8 or d 1 0 electron configuration.