[reaction: see text] The first total synthesis of an N,C-coupled naphthylisoquinoline alkaloid-ancisheynine-was achieved by condensing a monocyclic diketone or the respective benzopyrylium salt with an aminonaphthalene. The presence of a rotationally hindered axis in ancisheynine was demonstrated by resolution of its two atropo-enantiomers by HPLC on a chiral phase with LC-CD coupling. The assignment of their axial configurations succeeded by quantum chemical CD calculations.