A Merger of Relay Catalysis with Dynamic Kinetic Resolution Enables Enantioselective β‐C(sp3)−H Arylation of Alcohols.

The conceptual merger of relay catalysis with dynamic kinetic resolution strategy is reported to enable regio‐ and enantioselective C(sp3)‐H bond arylation of aliphatic alcohols, forming enantioenriched β‐aryl alcohols typically with >90 : 10 enantiomeric ratios (up to 98 : 2 er) and 36–74 % yields. The starting materials bearing neighbouring stereogenic centres can be converted to either diastereomer of the β‐aryl 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 Ru‐ and Pd‐complexes. Mechanistic experiments support the envisioned mechanism of the transformation occurring through a network of regio‐ and stereoselective processes operated by a coherent Ru/Pd‐dual catalytic system. [ABSTRACT FROM AUTHOR]