The traditional homogeneous access to aromatic amine derivatives is a nucleophilic aromatic substitution of the corresponding aryl halides. The halogen atom is usually relatively inert to amination reaction unless it is activated by the presence of electron withdrawing groups. Consequently, there has been particular emphasis over the past decade on the synthesis of metal complexes that are active catalysts for the preparation of aromatic amines. This tutorial review focuses on the use of metal-based complexes for the direct amination of aryl halides with ammonia.

Palladium-catalyzed transformations of aryl halides and pseudo-halides involving carbonylation, carbon–carbon and carbon–heteroatom bond-forming reactions, etc. are very well documented, and have already been reviewed several times. The metal-catalyzed activation of benzylic derivatives is much less described. However, during the last decades, a number of papers have shown the interest offered by benzylic derivatives (halides, carbonates, acetates, phosphonates) in selective catalytic reactions for organic synthesis, most of them in the presence of palladium catalysts. The purpose of this tutorial review is to highlight selected examples of palladium-catalyzed transformations involving reactive benzylic derivatives.