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. Enantioselective [2+2] cycloaddition reaction of azabenzonorbornadienes and oxabenzonorbornadienes with internal alkynes has been accomplished using Ni(COD)2/(R)‐SIPHOS‐Ph‐Mor catalytic system. This transformation represents a straightforward method to prepare four‐membered carbocycles.