ZnCl2‐Catalyzed [4+1] Annulation of Alkylthio‐Substituted Enaminones and Enaminothiones with Sulfur Ylides

Abstract Concise construction of furan and thiophene units has played an important role in the synthesis of potentially bioactive compounds and functional materials. Herein, an efficient Lewis acid ZnCl 2 catalyzed [4+1] annulation of alkylthio‐substituted enaminones is reported, that is, α‐oxo ketene N,S‐acetals with sulfur ylides to afford 2‐acyl‐3‐aminofuran derivatives. In a similar fashion, [4+1] annulation of the corresponding enaminothiones, that is, α‐thioxo ketene N,S‐acetals, with sulfur ylides efficiently proceeded to give multisubstituted 3‐aminothiophenes. This method features wide substrate scopes as well as broad functional group tolerance, offering a concise route to highly functionalized furans and thiophenes.