In recent years, the chemistry of hypervalent iodine compounds experienced an immersive grow resulting in a plethora of applications in organic synthesis, including the oxidation of alcohols, CH-oxidations and phenol dearomatizations. Besides their remarkable reactivity as dehydrogenative oxidants, in particular aryl-λ 3 -iodanes turned out to be potent electrophilic group transfer reagents. The most prominent representatives are diaryliodonium salts as electrophilic arylating reagents, alkenyl(aryl)iodonium salts as electrophilic vinyl motives and alkynyl(aryl)iodonium salts for electrophilic alkyne transfer reactions. In the latter, thermal stability is a latent problem. Here, intermolecular stabilization by oxygenbased donors in the form of ethynyl-benziodoxol(on)es (EBX) revealed a significantly increased thermal stability and hence an improved synthetic utilization of alkynyl-substituted iodanes (Figure ). Figure : Pseudocyclic and cyclic TIPS-ethynyl N-heterocycle-substituted-λ