Abstract:In the last fifteen years, gold has raised from the status of an inert noble metal to one of the most often used catalyst in synthetic chemistry. The functionalization of the triple bond of alkynes has been especially successful in this respect. In contrast, gold-catalyzed alkynylation methods have begun to emerge only in 2007. Since then, three different approaches have been successful. Gold nanoparticles allowed catalytic cycles based on oxidative arylation on aryl halides to give a "palladium-free Sonogashira reaction". The use of benziodoxol(on)e hypervalent iodine compounds as oxidative alkynylation reagents had then allowed the C-H functionalization of electron-rich heterocycles under mild conditions and with a very broad functional group tolerance. Finally, the use of iodobenzene acetate or Selectfluor as external oxidant led to the first alkynylation methods based on direct C-H/C-H coupling. In only six years, gold-catalyzed alkynylation methods have raised from nonexistent to useful synthetic protocols for the synthesis of structurally diverse alkynes. When considering that acetylenes are among the most important building blocks for applications in synthetic chemistry, chemical biology and materials science, a tremendous potential for further development of gold-catalyzed alkynylation can be expected for the future.