5-Arylpyrrolidine-2-carboxylates with an ortho-halogen substituent at 5-aryl and an electron-withdrawing group
at the C4 position of the pyrrolidine ring were transformed
into 1H-benzo[b]azepine-2-carboxylates
under Cu(I) promotion and microwave activation. Reaction promoter
copper(I) thiophene-2-carboxylate has been generated in situ in the reaction’s environment from Cu2O and thiophene-2-carboxylic
acid. Functionalized 1H-benzo[b]azepine-2-carboxylates
were obtained in racemic and optically active forms in 67–89%
yields. Subsequent stereoselective 1,3-dipolar cycloaddition and an
Ullmann-type annulation/rearrangement cascade (UARC) ensure a synthetic
route to oligomeric optically active benzazepine species with a well-defined
3D-structure.