Enantiodivergent Desymmetrization in the Rhodium( III)-Catalyzed Annulation of Sulfoximines with Diazo Compounds

Rh-III- and Ir-III-catalyzed asymmetric C-H functionalization reactions of arenes have relied on the employment of chiral Rh-III/Ir-III cyclopentadienyl catalysts, the introduction of chiral carboxylic acids to achiral Cp*RhX2 catalysts, and the integration of both strategies. Despite considerable progress, each reaction only provided a specific configuration of the enantioenriched product when using a particular chiral catalyst. Reported in this work is the enantiodivergent coupling of sulfoximines with various diazo compounds by Rh-III-catalyzed desymmetrizing annulation. The enantiodivergence was enabled by a judicious choice of achiral carboxylic acids, and the enantioselectivity correlates with the steric bias of the carboxylic acid and the sulfoximine.