Rhodium‐Catalyzed, Highly Enantioselective 1,2‐Addition of Aryl Boronic Acids to α‐Ketoesters and α‐Diketones Using Simple, Chiral Sulfur–Olefin Ligands

Simply the best: The title reaction has been achieved by asymmetric rhodium catalysis employing an extremely simple, chiral N-(sulfinyl)cinnamylamine ligand. A variety of highly enantioenriched, tertiary α-hydroxy carbonyl derivatives were easily accessed at room temperature under mild conditions with enantioselectivities of up to 99 %.