Regio- and Stereoselective Chlorocyanation of Alkynes

Abstract

A variety of terminal and internal alkynes were converted regio- and stereoselectively into (Z)-3-chloroacrylonitriles by treatment with BCl₃ in the presence of stoichiometric amounts of imidazolium thiocyanates. These products could be readily functionalized to provide useful building blocks, thus demonstrating the synthetic value of the method. Preliminary mechanistic studies suggest initial activation of the cationic thiocyanate by the Lewis acid, followed by electrophilic attack of the alkyne. The syn addition of a chloride to the vinyl cation intermediate and final elimination of the thiourea unit afford the desired chloroacrylonitriles.

Keywords: alkynes; chlorocyanation; electrophilic cyanation; nitriles; stereoselectivity.