As a consequence, we recently disclosed an enantioselective Pd-catalyzed aryl-carbonylation of sulfonimidamides with aryl and heteroaryl iodides (Figure ). This reaction leveraged the rapid tautomerization of the imido and amido nitrogens on unprotected sulfonimidamide starting materials, which provided a unique opportunity to desymmetrize the prochiral nitrogens via dynamic kinetic resolution. Additionally, Willis and coworkers have reported an enantioselective alkylation of protected sulfonimidamides using cinchona alkaloid-derived phase-transfer Standard reaction conditions: 1a (0.16 mmol, 1.0 equiv), 2a (0.48 mmol, 3.0 equiv), and catalyst 3 (0.032 mmol, 20 mol %) in THF (3.2 mL, 0.05 M) at -35 °C. a Relative product area % as determined by SFC analysis. Enantiomeric ratio (er) of product in the crude reaction mixture as determined by chiral SFC analysis. catalysts. With the desire to expand the number of enantioselective transformations and to gain convenient access to the chiral sulfonimidamide pharmacophore, we have investigated direct desymmetrization through acylation with a labile electrophile and a cinchona alkaloid for nucleophilic catalysis. This resolution of the two unprotected nitrogen nucleophiles on a single sulfur chiral center is challenging due to the tendency towards oligomeirzation and the lack of obvious structural differences required for effective catalyst recognition. Additionally, the nitrogens in both the starting material and mono-acylated product are nucleophilic, which can result in competitive uncatalyzed reactions and the ability to form bis-acylated product (as observed in reported aryl-carbonylation reactions). Related enantioselective acylation of nitrogen nucleophiles are sparse but include both enzymatic and small molecule catalysis, highlighted by independent efforts of the Seidel, Fu, and Bode 14 teams.