When HCl is liberated under equilibrium, the spatial proximity facilitates the efficient electrophilic addition of HCl to the ethynyl group affording the corresponding chloroalkene without overaddition. Keywords: Alkynes; Amines; Electrophilic addition; Pseudo-intramolecular process; Synthetic methods EN Alkynes Amines Electrophilic addition Pseudo-intramolecular process Synthetic methods 5746 5746 1 11/18/21 20211115 NES 211115 B The Front Cover b shows pseudo-intramolecular hydrochlorination of ethynylaniline, which proceeds efficiently in I syn i -selective and regioselective mode even in the absence of any metal catalyst. Alkynes, Amines, Electrophilic addition, Pseudo-intramolecular process, Synthetic methods. [Extracted from the article]