A four step asymmetric synthesis of 1,4-di- and 1,1,4-trisubstituted enantiomerically pure tetrahydro-3-benzazepines is described. Tricyclic oxazolobenzazepinones trans- 9 and cis- 10 allow the introduction of different alkyl groups (methyl, ethyl, allyl) with high diastereoselectivity (dr >99:1). The relative configuration of the new stereogenic center was determined by NOE experiments. Tricyclic lactams trans- 9 and cis- 10 were also used for the introduction of two substituents and, moreover, the establishment of spirocyclic rings. Reduction of the substitution products 11 and 12 with AlCl 3/LiAlH 4 (1:3) took place with retention of configuration and the final hydrogenolytic removal of the N-(2-hydroxy-1-phenylethyl) residue provided enantiomerically pure 1,4-di- and 1,1,4-trisubstituted tetrahydro-3-benzazepines 17 and ent- 17. In receptor binding studies with radioligands, the 3-benzazepines 17a–g and ent- 17a–g did not show any interactions with σ 1, σ 2 or NMDA receptors.