Reagent-Regulated Organocatalytic Enantiodivergent Synthesis of Chiral Sulfinimidate Esters

-chlorophthalimide (NCP) and trichloroisocyanuric acid (TCCA) with the same enantiomer of chiral pentanidium catalyst, and both enantiomers of sulfinimidate esters are obtained with high enantiocontrol. Notably, the reactions with TCCA are very fast and completed in 5 min, and the efficiency is well maintained for gram-scale synthesis. The resulting sulfinimidate esters are versatile precursors for diverse aza-S(IV) and S(VI) stereogenic centers. Studies on the enantiodivergent mechanism reveal that the sulfur stereogenic center is inverted twice in reactions with NCP, and only a single inversion is verified with TCCA, representing a novel strategy for enantiodivergent catalysis.