(ItPe)AuBr2(N-imidate) complexes, prepared in high yield by oxidative bromination, are active catalysts for 1,5-enyne cycloisomerization. An efficient tandem nucleophilic substitution–1,5-enyne cycloisomerization is promoted by these novel Au(III) precatalysts. Catalyst efficacy is affected by the imidate ligand and the silver salt used (e.g. Ag[Al(OC(CF3)3)4]).