Rhodium-catalyzed 1,3-acyloxy migration and subsequent intramolecular [4+2] cycloaddition of vinylallene and unactivated alkyne.

A Rh-catalyzed 1,3-acyloxy migration of propargyl ester followed by intramolecular [4+2] cycloaddition of vinylallene and unactivated alkyne was developed. This tandem reaction provides access to bicyclic compounds containing a highly functionalized isotoluene or cyclohexenone structural motif, while only aromatic compounds were observed in related transition metal-catalyzed cycloadditions.