A new synthetic pathway has been developed for the preparation of imine-containing pyrrolo [2, 1-c][1, 4] benzodiazepines (PBDs) and their dimers. Selective reduction of aromatic azides as well as aliphatic amides in a single step leading to an intramolecular reductive cyclization process by employing LiAlH4 or LiBH4 provides the cyclized imines.