Dinickel‐Catalyzed Enantioselective <i>α</i> ‐Amination of Ketones With Aliphatic Amino Group

Enantioselective α ‐amination of ketones represents a straightforward strategy for synthesizing highly valuable chiral α ‐amino ketones. However, most existing methods install a masked amino group, requiring additional steps to reveal the free amine. Consequently, the direct introduction of a simple alkylamino group at the ketone α ‐position remains underdeveloped. Herein, we report a dinickel‐catalyzed enantioselective α ‐amination of simple ketones that directly constructs chiral α ‐tertiary secondary amines. This reaction proceeds in moderate to good yield with good enantioselectivity via an S N 2 nucleophilic substitution at nitrogen by a dinickel enolate.