In Quest of Factors That Control the Enantioselective Catalytic Markovnikov Hydroboration/Oxidation of Vinylarenes

This study attempts to rationalise the unpredictable performance of transition metal catalysed asymmetric hydroboration of vinylarenes on varying the precursor of the catalyst from cationic to neutral species, [M(cod)( L– L)]BF 4 , [M(μ‐Cl)(cod)] 2 /(L–L), the metal (M=Rh and Ir), and the hydroborating reagent (catecholborane, pinacolborane). The approaches are based on the agreement between experimental data provided by ( R )‐Binap and ( R )‐Quinap modified catalytic systems and computational data evidenced by DFT calculations and QM/MM strategies. Unprecedentedly high enantiomeric excesses in the hydroboration/oxidation of vinylarenes with both electron‐withdrawing substituents (( R )‐(+)‐1‐ p ‐F‐phenylethanol, ee up to 92 %) and electron‐releasing substituents (( R )‐(+)‐1‐ p ‐MeO‐phenylethanol, ee up to 98 %), can be attributed to a rhodium halide key intermediate.