Enantioselective Palladium(II)‐Catalyzed Desymmetrizative Coupling of 7‐Azabenzonorbornadienes with Alkynylanilines

Abstract A Pd II ‐catalyzed, domino enantioselective desymmetrizative coupling of 7‐azabenzonorbornadienes with alkynylanilines is disclosed herein. This operationally simple transformation generates three covalent bonds and two contiguous stereocenters with excellent enantio‐ and diastereo‐selectivity. The resulting functionalized indole‐dihydronaphthalene‐amine conjugates served as an appealing platform to streamline the diversity‐oriented synthesis (DOS) of other valuable enantioenriched compounds. DFT calculations revealed that the two stabilizing non‐covalent interactions contributed to the observed enantioselectivity.