Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalyticquantity (3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene ofunprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yieldsup to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials asthe limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates aswell as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bondsor sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursorand the chiral catalyst at the origin of these good results have also been applied to kinetic resolution ofracemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as syntheticprecursors for the introduction of a nitrogen functionality into selected positions.