PyBidine/Copper Catalyst: Asymmetric exo′‐Selective [3+2] Cycloaddition using Imino Ester and Electrophilic Indole

Electrophilic indoles having two electron‐withdrawing groups undergo nucleophilic attack at C2 and electrophilic functionalization at C3. This is the first enantioselective formal 3+2] cycloaddition using electrophilic indoles. The PyBidine/Cu catalyst smoothly promoted highly enantio‐ and exo′‐selective 3+2] cycloaddition using imino esters and 3‐nitroindoles. This reaction provides a method for the preparation of diverse and complex chiral pyrroloindoline compounds.