Synthesis of Enantioenriched Primary tert-Butanesulfonimidamides via Imination–Hydrazinolysis of N′-tert-Butanesulfinyl Amidines

The first synthesis of primary tert-butanesulfonimidamides with high enantiopurity was realized by imination (or imination/N-functionalization) of enantioenriched N′-tert-butanesulfinyl amidines, followed by hydrazinolysis. N′-Sulfinyl amidines served as imination precursors during copper-catalyzed sulfonyl nitrene transfer or iodonitrene-based NH transfer. Further transformations allowed access to primary tert-butanesulfonimidamides with diverse substitutions on the nitrogen of S═N.