Structurally related to iodosylbenzene PhI=O, iodonium imidesPhI=NR, off-white to pale yellow solids of low solubility, belongto the class of hypervalent iodine(III) reagents and were first preparednearly thirty years ago. Two additional decades were needed beforethey could be considered as useful nitrene precursors with the discoveryof the copper-catalyzed aziridination of olefins. Since then, iminoiodaneshave been successfully applied in the total synthesis of naturaland/or biologically active compounds. Recent developmentsaimed at circumventing their tedious preparation led to the discoveryof one-pot nitrogen transfers from sulfonamides, sulfamates, orcarbamates mediated by iodosylbenzene(diacetate) PhI(OAc)2 oriodosylbenzene. Reliable functionalizations of alkanes and alkenesvia C-H insertion or aziridination using copper or rhodiumcatalysts can now be considered as synthetically useful processes.