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Dynamic Kinetic Asymmetric Transformations of β‐Stereogenic α‐Ketoesters by Direct Aldolization
Author(s) -
Corbett Michael T.,
Johnson Jeffrey S.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201306873
Subject(s) - nitromethane , stereocenter , aldol reaction , chemistry , racemization , adduct , acetone , yield (engineering) , enantioselective synthesis , catalysis , organic chemistry , materials science , metallurgy
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.