One-pot syntheses of dihydro benzo[b][1,4]thiazepines and -diazepines via coupling-isomerization-cyclocondensation sequences

2,4-Di(hetero)aryl substituted 2,3-dihydro benzo[b][1,4]heteroazepines 7 and 9 (hetero=S, NH) can be readily synthesized in a one-pot process initiated by a coupling-isomerization sequence of an electron poor (hetero)aryl halide 4 and a terminal propargyl alcohol 5 subsequently followed by a cyclocondensation with 2-mercapto or 2-amino anilines 6 or 8, respectively. In addition, the structures were established unambiguously by an X-ray structure analysis of 9b. (C) 2004 Elsevier Ltd. All rights reserved.