Deprotonative generation of cyclohexynes, cycloheptynes, and cyclooctynes was achieved by controlling the reactivities of transient anionic species from the corresponding enol triflates with magnesium bis(2,2,6,6-tetramethylpiperidide) as a base. The starting enol triflates are readily obtained through triflation of the corresponding ketones, allowing direct access to the cycloalkynes.