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.
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA) http://www.unc.edu/jsjgroup/Home.html.
Michael T
MT
Corbett
Jeffrey S
JS
Johnson
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
D000447:Aldehydes; D004952:Esters; D007659:Ketones
DyKAT; Henry reaction; acetone aldol reaction; organocatalysis; α-ketoesters