The imidation of sulfides and sulfoxides to the corresponding intermediate (nitrene)Fe IV complex is postulated as the reactive nitrene transfer reagent which is formed from FeCl 2 sulfimides and sulfoximides was carried out with N-tertbutyloxycarbonyl azide (BocN 3 ) in the presence of FeCl 2 .
and BocN 3 . The more nucleophilic sulfides 2 reacted more readily in the imidation than sulfoxides. Their conversion to Sulfoxides 1 reacted at room temperature in CH 2 Cl 2 to give the corresponding sulfoximides 3 in 40-95% yield. The the corresponding sulfimides 4 was conducted with BocN 3 and a substoichiometric amount of FeCl 2 (0.25 equiv.). Yields imidation of the sterically congested substrate tert-butyl methyl sulfoxide (1f) proceeded sluggishly (10% yield). The ranged between 44 and 92%. In an alternative reaction mode, BocN 3 was utilized at 0°C in the presence of FeCl 2 sterospecificity of the reaction was demonstrated with the enantiomerically enriched substrates (R)-(+)-1b and (S)-(-)-and acetyl acetone. The sulfimidation, which did not otherwise occur at this temperature, was accelerated by the 1d which yielded the sulfoximides (R)-(+)-3b and (S)-(-)-3d with retention of configuration. Mechanistically, an ligand (36-90% yield).