The intermolecular 1,3-diamination reaction of readily available alkenes with N-fluorobis(benzenesulfonamides) catalyzed by rhodium(II) is reported herein. The isomers of the terminal and internal alkenes, even mixtures, all provided the same allylic 1,3-diamine products under mild reaction conditions. The resulting diaminated products can be derived to functionalized diamines and can further generate allylic triamines. Mechanistic studies revealed that the rhodium(II) compounds catalyzed a variety of chemical transformations during the reactions based on their single-electron redox catalytic cycle, specifically radical polarity crossover in terminal alkenes and the direct activation of allylic C−H bonds followed by radical cross-coupling in the internal alkenes. These results show the potential of rhodium(II) in C−H amination reactions in addition to the well-known transformations of rhodium nitrenoids.

1,3‐Diamines are important for many biologically active molecules, but there have been fewer studies on the synthesis of 1,3‐diamines than those on the synthesis of 1,2‐diamines. Relatively speaking, there are not sufficient reports on non‐catalytic methods in this direction. Among various methods, the catalytic construction of diamine products from nitrogen‐containing substrates is the most straightforward, but it suffers from the need to pre‐synthesize nitrogen‐containing substrates and is therefore narrowly used. For non‐specialized substrates, the direct construction of C−N bonds by metal‐ or non‐metal‐catalyzed C−H functionalization is undoubtedly the most efficient approach. This method is currently focused on monofunctionalization, but less has been reported for the simultaneous construction of multiple C−N bonds. Here, we summarize some innovative methods for the synthesis of 1,3‐diamines that have been developed in the past five years, encompassing various directions such as non‐catalytic reaction and metal‐ or non‐metal catalyzed reaction.