Enhancing Reactivity and Selectivity of Aryl Bromides: A Complementary Approach to Dibenzo[<i>b,f</i>]azepine Derivatives

Abstract Dihydrodibenzo[ b , f ]azepines and dibenzo[ b , f ]azepines can be efficiently synthesized from aryl bromides, o ‐bromoanilines and norbornene or norbornadiene by means of palladium catalysis. This protocol gives access to dibenzo[ b , f ]azepine core containing a variety of electron‐withdrawing substituents on both aromatic rings and complements the previously reported methodology where electron rich aryl iodides were preferentially used. The presence of KI, even in sub‐stoichiometric amount, is crucial for this three‐component reaction. The proper addition of iodide anions has a dramatic effect on reaction rate and selectivity. A formal three‐step synthesis of the tricyclic antidepressant Clomipramine (Anafranil ® ) is also described.