Catalytic Electrophilic Halogenation of Silyl‐Protected and Terminal Alkynes: Trapping Gold(I) Acetylides vs. a Brønsted Acid‐Promoted Reaction

In the presence of a cationic gold(I) catalyst and N ‐halosuccinimide, both trimethylsilyl‐protected and terminal alkynes are converted into alkynyl halides. Further experiments showed that silyl‐protected alkynes undergo electrophilic iodination and bromination under Brønsted acid catalysis, whilst terminal alkynes require a cationic gold catalyst. The former reactions probably proceed via activation of the electrophile, whilst the latter reactions proceed via a gold(I) acetylide intermediate. Gold‐catalysed halogenation was further combined with gold‐catalysed hydration and subsequent annulation to provide convenient routes to iodomethyl ketones and five‐membered aromatic heterocycles.