Special Issue: Selected Papers from the 2(nd) International Conference on Natural Products and Physiologically Active Substances (ICNPAS-2004) and the 3(rd) EuroAsian Heterocyclic Meeting “Heterocycles in Organic and Combinatorial Chemistry” (EAHM-2004)

A general and highly efficient protocol for the synthesis of dibenzodiazepines and their structural analogues is reported. In the presence of catalytic quantities of palladium, readily accessible precursors are cross-coupled with ammonia and then spontaneously undergo an intramolecular condensation to form the corresponding dibenzodiazepines in one step. This new strategy is applicable to the construction of a wide variety of dibenzooxazepines and other structurally related heterocycles.