Diastereoselective and Reversed Regioselective Annulations of N-Alkyl Anilines to Julolidines and Lilolidines.

A three-component annulation reaction of N-alkyl anilines, cyclic 1,3-dicarbonyl compounds, and aryl aldehydes to julolidines and lilolidines is reported. The 6π-electrocyclization enabled the annulation to proceed with reversed regioselectivity as compared with the annulation that occurs in the Povarov reaction. Both cyclic and acyclic N-alkyl anilines participated in the reaction to provide a wide range of julolidines and lilolidines as the single regio- and diastereoisomers in good to excellent yields.