Abstract The alkynylperfluoroalkanesulfones 5a–e have been prepared and their cycloaddition reactivity towards dienes and diazomsthane has been studied. The faster reaction rate of 5b with cyclopentadiene than 5a and vice versa with tetracyclone (6) has been explained on steric and electronic affects. The alkynylperfluoroalkanesulfones are very reactive towards nucleophilic additions. Attempts to prepare the highly reactive bis- ...