Desymmetrization of Heterocyclic Sulfonimidamides via Asymmetric Tsuji-Trost Asymmetric Alkylation

Methodologies enabling the synthesis of enantioenriched sulfonimidamides containing a stereogenic sulfur center are scarce, often relying on diastereomeric crystallization or the use of chiral auxiliaries. The prototropic tautomerization exhibited by sulfonimidamides makes them uniquely suited for resolution processes. In the case where both nitrogen substituents of a disubstituted sulfonimidamide are the same, the two tautomers are also enantiomers, allowing deprotonation to generate a prochiral anion. Herein we report the first transition metal-catalyzed approach to the desymmetrization of sulfonimidamides relying on commercially available palladium catalysts and ligands. The reaction leads to functionalized, enantioenriched products in high yields.