Transition‐Metal‐Catalyzed Cross‐Coupling and Sequential Reactions of Azides with Isocyanides

Abstract Transition‐metal‐catalyzed cross‐coupling reaction of azides with isocyanides, as a new type of nitrene transformation, has become an expeditious method to prepare carbodiimides. Considering the compatibility of this coupling process with other systems, transition‐metal‐catalyzed sequential reactions have become more popular in recent years. These remarkable advances not only involve many interesting reaction processes, but also provide useful strategies for the construction of nitrogen‐containing structures, such as guanidines, amidines, isoureas, and heterocyclic compounds. This review will present a comprehensive picture of the development of transition‐metal‐catalyzed coupling process of azides with isocyanides and their applications in the preparation of nitrogen‐containing compounds. Catalytic coupling reactions followed by nucleophilic additions will be briefly introduced here. Most recent advances in catalytic cascade reactions involving a coupling process will be highlighted and make up the main part of this review. magnified image