Dynamic kinetic asymmetric transformations of β-stereogenic α-ketoesters by direct aldolization

Dynamic kinetic asymmetric transformations (DyKAT) of racemic β-bromo-α-keto esters by direct aldolization of nitromethane and acetone provide access to fully substituted α-glycolic acid derivatives bearing a β-stereocenter. The aldol adducts are obtained in excellent yield with high relative and absolute stereocontrol under mild reaction conditions. Mechanistic studies determined that the reactions proceed through a facile catalyst-mediated racemization of the β-bromo-α-keto esters under a DyKAT Type I manifold.