Iridium‐Catalyzed Asymmetric β‐Selective Hydroamination of Enamides for the Synthesis of 1,2‐Diamines

Abstract

Abstract An iridium‐catalyzed highly enantioselective hydroamination of electron‐rich alkenes has been developed. The coordination assistance of the amide group to the metal center effectively overrides the inherent electronic preference of N─H addition to an enamide, delivering unconventional β‐selectivity. Phthalimide is utilized as a readily removable amination agent. This methodology enables direct access to enantio‐enriched 1,2‐diamines from readily available materials with 100% atom economy, exclusive regioselectivity, and excellent enantioselectivity (up to 99% ee).