Sulfoximine <i>N</i> -Functionalization with <i>N</i> -Fluorobenzenesulfonamide

An operationally simple, convenient, mild, metal-free, and scalable transformation of sulfoximines with <i>N</i>-fluorobenzenesulfonamide is presented. A wide range of structurally different <i>N</i>H-sulfoximines were prepared and reacted with <i>N</i>-fluorobenzenesulfonamide in the presence of TMP (2,2,6,6-Tetramethylpiperidine) and in the environmentally friendly EtOAc to obtain the desired products, mostly in yields above 75%. The method also supports various amine, hydrazide, phenol, and amino acid substrates as well as scale-up to gram reactions with minimal to no modification of the process. The products formed from the sulfoximines were structurally analyzed by NMR and X-ray crystallography and investigated for their stability and further reactivity as substrates in Suzuki-Miyaura coupling, methylation, and bromination reactions. In addition, DFT calculations were carried out with regard to the energy profile and mechanism of the reaction.