Vicinal diamines are the central structural motifs of a wide variety of biologically active molecules, natural products, and pharmaceuticals (Fig. ). Moreover, these diamine frameworks are also frequently employed as organocatalysts, and privileged ligands for transition-metal catalysis. Among various synthetic approaches to vicinal diamines, the catalytic diamination/diazidation of carbon-carbon double bonds is generally regarded as one of the most efficient and straightforward methods and has been of great interest to synthetic chemists. Despite significant achievements made in the past few decades, some fundamental issues still remain to be solved in this field. First, the majority of these methods require transition-metals or hyper-valent iodine reagents as catalysts. In addition, the utilization of stoichiometric amounts of metal reagents (e.g. osmium or cobalt), chemical oxidants, or azide reagents, leads to the issues on cost, environment, and safety. Second, the established protocols are often limited to symmetrical diamination, namely installing two undifferentiated amino functionalities across alkenes.