The microwave-assisted cycloaddition of 2,6-disubstituted benzonitrile oxides to 1-iodobuta-1,3-diynes occurs at the iodo-substituted triple bond giving predominantly 5-alkynyl-4-iodo-1,2,3-isoxazoles. The Suzuki–Miyaura and Sonogashira cross-coupling reactions were used for the modification of the thus obtained 4-iodoisoxazoles.