Counteranion-controlled regioselectivity in palladium-catalyzed allylic amination of dienyl allylic carbonates

A regioselective Pd-catalyzed allylic amination reaction of dienyl allylic carbonates and aromatic amines has been developed by means of phosphoramidite-palladium catalysis. The regioselectivity could be altered by the counterion of the π-allylpalladium intermediate. As a result, either branched Z-dienyl allylic amines or linear conjugated allylic amines were generated in high levels of regioselectivity from the same substrates by tuning the reaction conditions.