Transition‐Metal‐Catalyzed Denitrogenative Annulation to Access High‐Valued N‐Heterocycles

Over the past few years, the development of efficient methods to construct high‐valued N‐heterocyclic molecules have received massive attention owing to their extensive application in the areas of medicinal chemistry, drug discovery, natural product synthesis and so on. To access those high‐valued N‐heterocycles, many methods have been developed. In this context, transition‐metal‐catalyzed denitrogenative annulation of 1,2,3‐triazoles and 1,2,3,4‐tetrazoles has appeared as a powerful synthetic tool because it offers a step‐ and atom‐economical route for the preparation of the nitrogen‐rich molecules. Compared with the denitrogenative annulation of various 1,2,3‐triazole frameworks, annulation of 1,2,3,4‐tetrazole remains more challenging due to the inertness of the tetrazole moiety. This Review summarizes the significant achievements made in the field of denitrogenative annulation of various 1,2,3‐triazoles and 1,2,3,4‐tetrazoles including some pioneering examples in this area of research. We anticipate that this denitrogenative annulation reaction will find broad applications in the pharmaceutical industry, drug discovery and other fields of medicinal chemistry. Transition‐metal‐catalyzed denitrogenative annulation is a unique concept that has provided a new dimension for the construction of high‐valued nitrogen heterocycles. This Review highlights the denitrogenative annulation concept applied to various 1,2,3‐triazoles and 1,2,3,4‐tetrazoles.