In recent years, the non‐covalent interaction of halogen bonding (XB) has found increasing application in organocatalysis. However, reports of the activation of metal‐ligand bonds by XB have so far been limited to a few reactions with elemental iodine or bromine. Herein, we present the activation of metal‐halogen bonds by two classes of inert halogen bond donors and the use of the resulting activated complexes in homogenous gold catalysis. The only recently explored class of iodolium derivatives were shown to be effective activators in two test reactions and their activity could be modulated by blocking of the Lewis acidic sites. Bis(benzimidazolium)‐based halogen bonding activators provided even more rapid conversion, while the non‐iodinated reference compound showed little activity. The role of halogen bonding in the activation of metal‐halogen bonds was further investigated by NMR experiments and DFT calculations, which support the mode of activation occurring via halogen bonding.

Despite attracting tremendous interest over the last few decades, the field of electrophilic cyclizations is still continuously and rapidly developing. Particularly, metal-free reactions that involve the activation of an alkyne using electrophilic halogen sources are powerful tools in the repertoire of synthetic chemists. This brief overview highlights recent progress in C–C bond-forming halocyclizations allowing for the reaction of alkynes with carbon-nucleophiles. Primarily guided by the type of carbon nucleophile, methods are categorized as the addition of arene, malonate, and olefin nucleophiles.