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

Abstract 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*RhX 2 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.