The unexpected domino coupling and rearrangement of the Cinchona alkaloid skeleton has been found to occur in the reaction of 9-chloro-9-deoxy-alkaloids with Grignards from peri-dihalogenonaphthalene. The cyclization and migration of the central quinuclidinylmethyl group (C9) from position C-4' to position C-3' of quinoline formed a novel chiral ring system of 5-aza-7H-benzo[no]tetraphene, yielding products of unlike configuration. The proposed reaction pathway involves radical intermediates.