Nickel‐Catalyzed Asymmetric [2+2] Cycloaddition Reaction of Hetero‐Bicyclic Alkenes with Internal Alkynes

: Enantioselective [2+2] cycloaddition reaction of azabenzonorbornadienes and oxabenzonorbornadienes with internal alkynes has been enabled by a catalyst system comprising Ni(COD)2 and (R)-SIPHOS-Ph-Mor. This transformation represents the first asymmetric [2+2] cycloaddition reaction of azabenzonorbornadienes with internal alkynes, providing a straightforward method to prepare four-membered carbocycles.