Enantioselective Synthesis of Sulfinamidines via Asymmetric Rhodium–Catalyzed Imidation of Sulfenamides

The asymmetric preparation of S(IV) and S(VI) compounds is a topic of great interest due to the increasing use of these structures in drug discovery and organic synthesis. In this context, the stereoselective synthesis of sulfinamidines, the aza‐S(IV) analogues of sulfinamides, remains largely underexplored. Herein, the study reports the preparation of enantioenriched sulfinamidines via the catalytic asymmetric imidation of sulfenamides using a chiral dirhodium(II) tetracarboxylate catalyst. This method enables the imidation of N , N ‐bisalkyl sulfenamides with yields of up to 98% and with enantiomeric ratios up to 98:2, employing a catalyst loading of only 1 mol%. Importantly, subsequent stereospecific oxidation of the sulfinamidine leads to the corresponding enantioenriched sulfonimidamide, a valuable aza‐S(VI) motif with applications in medicinal chemistry and agrochemistry.