Rh III -and Ir III -catalyzed asymmetric C À Hfunctionalization reactions of arenes have relied on the employment of chiral Rh III /Ir III cyclopentadienyl catalysts,t he introduction of chiral carboxylic acids to achiral Cp*RhX 2 catalysts,a nd the integration of both strategies.D espite considerable progress, each reaction only provided as pecific configuration of the enantioenriched product when using ap articular chiral catalyst. Reported in this work is the enantiodivergent coupling of sulfoximines with various diazoc ompounds by Rh IIIcatalyzedd esymmetrizing annulation. The enantiodivergence was enabled by aj udicious choice of achiral carboxylic acids, and the enantioselectivity correlates with the steric bias of the carboxylic acid and the sulfoximine.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Copper hydride-catalyzed asymmetric hydroamination of olefins with anthranils has been realized in high efficiency and high enantioselectivity, affording enantioenriched secondary arylamines tethered to a benzylic alcohol. The bifunctionality of the product has been employed in diverse derivatization reactions.