Acetylene gas is an important feedstock for chemical production, although it is underutilized in organic synthesis. We have developed an intermolecular gold(I)-catalyzed alkyne/alkene reaction of o-allylphenols with acetylene gas that gives rise to chromanes by a stereospecific aryloxycyclization through the nucleophilic regioselective opening of cyclopropyl gold(I)-carbene intermediates. The synthetic application of this method was demonstrated in the late-stage functionalization of the natural product lapachol.