Rhodium(II)-Catalyzed Allylic 1,3-Diamination
Beiqi Yang, Xinyu Liu, Aiwen Yu, Qi Yang, Yuanhua Wang
Abstract
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.