Ni(II)-Catalyzed Site- and Regioselective α-Alkenylation of Cyclic Ketones with Alkenes

Herein, a nickel-catalyzed α-alkenylation reaction of asymmetric cyclic ketones at the sterically hindered α-position with alkenes is disclosed. The high regioselectivity might originate from the acid-catalyzed enolization reaction, selectively generating the thermodynamically favored enol. The nickel catalyst facilitates the preferential alkenylation of polysubstituted enolates rather than monosubstituted enolates, thereby reversing the conventional regioselectivity of alkenylation at the α-position of ketones. This method encompasses a broad range of applicable substrates of alkenes.