Nickel-Catalyzed Enantioselective Hydroboration of Enamides

Enantioselective hydroboration of alkenes has become a powerful strategy for the synthesis of enantioenriched alkylboron compounds. However, analogous reactions involving electron-rich internal alkenes, such as enamides, remain largely underdeveloped and mainly limited to precious rhodium catalysis. Herein, we reported the first nickel-catalyzed enantioselective hydroboration of unactivated enamides, affording medicinally valuable β-amino boronates with high regio- and enantioselectivity (>20:1 r.r. and up to 96% ee). This earth-abundant metal system employs commercially available metal catalysts and ligands and operates under mild conditions, providing a practical and efficient platform for synthetic and medicinal chemistry.