Quaternary stereocenters feature in many natural products and pharmaceuticals, yet their synthesis is often difficult. We report an enantioconvergent Suzuki-Miyaura-type cross coupling between arylboronic acids and racemic tertiary electrophiles to give products containing quaternary stereocenters. Mechanistic studies suggest that the very high levels of enantiomeric excess observed are due to a Rh-catalyzed dynamic kinetic asymmetric transformation.