Synthesis of 1-amino-1,2,3,14b-tetrahydro-4H-pyrido[1,2-d]dibenzo[b,f] [1,4]oxazepine and related compounds

The synthesis is described of the epimeric 1-amino-1,2,3,14b-tetrahydro-4H-pyrido [1,2-d] dibenzo [b,f]-[1,4]oxazepines 2 and their N-substituted analogues. The cis-amines 33, 36 and 38 were prepared from the ketone 31 by reduction of the corresponding oxime whereas the trans isomers 12, 50 and 51 were prepared from the 1-ethoxycarbonyl derivative 44 by Curtius degradation. Attempts to convert the trans alcohol 7 into the epimeric azido compound by an S(N)2 replacement reaction with sodium azide resulted in rearrangement to give the novel ring system, 14-azido-11-methoxy-1,2,14, 14a-tetrahydro-4H-pyrrolo[1,2-d] dibenzo[b,g][1,4]oxazocine 24 instead of the titled compounds.