Cationic Rhodium-Catalyzed Hydroboration: Investigations into Electronic and Ligand Effects; Lewis-Acid Reaction Acceleration and Regioselectivity Change
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Mechanistic aspects of the asymmetric rhodium catalyzed hydroboration of vinyl arenes with catecholborane (HBCat) and pinacolborane (HBPin) have been probed. Competition studies conducted with catalysts bearing asymmetric ligands Josiphos or Quinap reveal substituent effects of varying sensitivity correlating to Hammett parameter sigma. In reactions involving the Quinap ligand, rho-values of +1.97 and +1.02 are observed for HBCat and HBPin, respectively. In Josiphos-ligated systems, rho-values of +1.38 and -3.17 are observed, indicating that the reaction proceeds through differing mechanisms depending on the borane employed. Labeling experiments reveal differences in the reversibility of the hydride insertion step of reaction depending on the ligand and borane implemented in hydroboration. A new methodology has been developed for regioselective rhodium-catalyzed hydroboration of internal olefins with pinacolborane. The addition of co-catalytic Lewis acids results in the activation of cationic rhodium catalysts in chlorinated solvents. Increased catalytic activity and regioselectivity are observed under these conditions. For internal alkyl olefins, selectivity for non-isomerized secondary boronate esters was found originate from the non-coordinating solvents employed in the reaction. For aromatic olefins, increased regioselectivity and reaction acceleration are both effects of the Lewis acid additive. Study of the reaction revealed that these properties are linked to Lewis acid-base mediated heterolytic B-H bond cleavage of pinacolborane, and suggests that the reagent is transferred to the rhodium catalyst as borenium ion and hydride moieties. Inhibition studies confirmed that Lewis acid is required throughout the reaction and does not solely act as an initiator.