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

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 enantioenriched 1,2-diamines from readily available materials with 100% atom economy, exclusive regioselectivity and excellent enantioselectivity (up to 99% ee).