Palladium‐Catalyzed Aminoalkylative Cyclization Enables Modular Synthesis of Exocyclic 1,3‐Dienes

A novel and efficient palladium-catalyzed regioselective and stereodivergent ring-closing reaction of aminoenynes with aldehydes and boronic acids or hydrosilane is developed. This three-component reaction allows for the modular synthesis of a series of exocyclic 1,3-dienes bearing 5- to 8-membered saturated N-heterocycles. The reactions utilize a simple Pd-catalyst and work with broad range of aminoenynes, aldehydes and organometallic reagents under mild reaction conditions. The products represent useful intermediates for chemical synthesis due to the versatility of the conjugated diene. Preliminary mechanistic details of the method are also revealed.