The regio‐ and stereoselective nucleophilic addition of primary aliphatic amines to 2‐(1‐alkynyl)‐2‐alken‐1‐ones was found to proceed through double‐bond migration. In particular, this is a mild and atom‐economical route for the preparation of (Z)‐β‐enaminones having cycloalkene rings.

An oxocarbenium ion mediated cyclization of (Z)-1,3-diarylprop-2-yn-1-one O-methyloximes and 3-arylprop-2-yn-1-(2-methoxyphenyl)-1-ones resulted in regioselective formation of functionalized isoxazoles and chromones, respectively. Alkoxy(aryl)methyl group containing compounds were obtained in good and high yields.