Mechanochemical Iron‐Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N ‐Acyl Sulfonimidamides from Sulfinamides and Dioxazolones

A mechanochemical synthesis of sulfonimidamides by iron(II)-catalyzed exogenous ligand-free N-acyl nitrene transfer to sulfinamides is reported. The one-step method tolerates a wide range of sulfinamides with various substituents under solvent-free ambient conditions. Compared to its solution-phase counterpart, this mechanochemical approach shows better conversion and chemoselectivity. Mechanistic investigations by ESI-MS revealed the generation of crucial nitrene iron intermediates.