Stereoselective Pd-Catalyzed Remote Hydroamination of Skipped Dienes with Azoles

A novel palladium-catalyzed stereoselective remote hydroamination reaction is disclosed. A series of azoles and skipped dienes undergo the migratory allylic C-H amination in good yields and selectivities. A desymmetric migratory azolation process is also developed to highlight the reliability of the transformation. Preliminary mechanistic experiments corroborate the designed metal walking and allylic substitution cascade strategy via Pd-H catalysis, different from prior ligand-to-ligand hydrogen transfer pathway for conjugated dienes.