Palladium(II)-Catalyzed Enantioselective Ring Opening of Oxabenzonorbornadienes via Domino Aminopalladation of Alkynylanilines

We report herein a robust enantioselective ring opening coupling of oxabenzonorbornadienes via Pd(II)-catalyzed domino cyclization of alkynylanilines, which features the formation of three covalent bonds and two contiguous stereocenters with excellent enantio- and diastereoselectivity and a broad substrate scope. The good functional group tolerance of this domino desymmetrization strategy enables efficient late-stage transformation of natural product-derived alkynylanilines. The resulting indolated dihydronaphthols could serve as a valuable platform to streamline the diversity-oriented synthesis of other valuable enantioenriched tetrahydronaphthalene derivatives.