AbstractA palladium/(R)‐Binap catalyst for asymmetric ring opening reaction of azabenzonorbornadienes with amines was developed that afforded the corresponding substituted dihydronaphthalenes in good yields (up to 97%) with excellent enantioselectivities (up to >99% ee). To the best of our knowledge, this represents the first palladium‐catalyzed asymmetric ring opening reaction of azabenzonorbornadienes with heteronucleophiles.magnified image