Practical Synthesis of Allylic Heteroaromatic Amines via Pd‐Catalyzed Oxidative Amination of Olefins

Heteroaryl amines are prone to over coordination in the transition metal-catalyzed olefin oxidation reaction system, which hinders the smooth catalytic reaction. Herein, we report a general method for the direct C─N coupling between inactive olefins and primary and secondary heterocyclic aromatic amines under palladium catalysis, which is an important transition that has not yet been revealed. By employing commercially available palladium catalysts, quinone oxidants, and inexpensive monodentate phosphine ligands, the oxidative amination of diverse heteroaryl amines proceeds smoothly, delivering a broad range of allyl heteroaryl amines with excellent regio- and stereoselectivity. Notably, this strategy enables the late-stage modification of challenging biologically relevant molecules such as adenine and adenosine, further highlighting the practicality and synthetic utility of this reaction.