Palladium-Catalyzed Cascade Double CN Bond Activation: A New Strategy for Aminomethylation of 1,3-Dienes with Aminals

A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminals via double CN bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear ,-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct CN bond to furnish a cascade double CN bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed CN bond activation of aminal and the ,-unsaturated allylic amine was subsequently produced via palladium-catalyzed CN bond activation of the allylic diamines.