AbstractMethyl isopropenyl ether (1) has been metallated at low temperature with a 1:1 molar mixture ofn‐BuLi/t‐BuOK in THF‐hexane, and subsequently functionalized with a variety of electrophilic reagents. At temperatures higher than – 30°C, the metallated methyl isopropenyl ether (2) decomposes with formation of allene. When the suspension of2is allowed to warm up to room temperature in the presence of an additional equivalent ofn‐BuLi, the intermediary allene is converted into 1‐propynyllithium (2c), which reacts with propylthiocyanate to give 1‐propylthio‐1‐propyne (4). Some of the functionalization products were subjected to acidic hydrolysis affording the expec