Cycloheptynes and cyclooctynes were efficiently generated via a sulfoxide–magnesium exchange reaction of readily synthesized 2-sulfinylcycloalkenyl triflates. Cycloadditions between various ynophiles and the cycloalkynes generated by this method proceeded efficiently, providing an easy method to prepare a wide range of heterocycles fused with seven- or eight-membered carbocycles.

A facile method for preparing various functional cycloalkynes, including proteins incorporated with a cycloalkyne moiety, from the corresponding azides is developed. Treatment of diynes bearing strained and terminal alkyne moieties with a copper salt enabled terminal alkyne-selective click conjugation with azides, whereas a more azidophilic strained alkyne moiety was transiently protected from the click reaction via complexation with copper.