Rearrangements of Propargylic Esters Can Be Induced by Some Electrophiles

An electrophile-induced rearrangement of propargylic esters without need of transition catalysis is possible. In particular, this observation provides a mild, economic, and effective method for the introduction of benzyl ether derivatives to access functionalized alpha,beta-unsaturated ketones. Preliminary mechanistic studies suggest that this rearrangement undergoes an intramolecular 1,3-acyloxy shift.