Abstract: Selective intramolecular C—H amination via metalloradical activation of azides: synthesis of 1,3-diamines under neutral and nonoxidative conditions. One aspect of the present invention is the synthesis of 1,3-diamines by intramolecular C—H amination of sulfamoyl azides. More specifically, sulfamoyl azides may be selectively aminated via metalloradical activation of azides, preferably with Co(II) porphyrins. In a particularly preferred embodiment, the Co(II) porphyrin is a D2h-symmetric porphyrin.

Abstract: A highly effective Co(II)-based system has been developed for catalytic intramolecular C—H amination with phosphoryl azides without the need of terminal oxidant or other additives, resulting in the high-yielding production of cyclophosphoramidates with nitrogen gas as the by-product; additional features of this new catalytic system include the amination of primary C—H bonds and formation of 7-membered ring structures.