AbstractThe conceptual merger of relay catalysis with dynamic kinetic resolution strategy is reported to enable regioâ and enantioselective C(sp3)âH bond arylation of aliphatic alcohols, forming enantioenriched ÎČâaryl alcohols typically with >90 : 10 enantiomeric ratios (up to 98 : 2 er) and 36â74 % yields. The starting materials bearing neighbouring stereogenic centres can be converted to either diastereomer of the ÎČâaryl alcohol products, with >85 : 15 diastereomeric ratios determined by the catalysts. The reactions occur under mild conditions, ensuring broad compatibility, and involve readily available aryl bromides, an inorganic base, and commercial Ruâ and Pdâcomplexes. Mechanistic experiments support the envisioned mechanism of the transformation occurring through a network of regioâ and stereoselective processes operated by a coherent Ru/Pdâdual catalytic system.