The tertiary amine-catalyzed direct asymmetric aldol reac-
tion of 2-hydroxyacetophenones (2-hydroxy-1-arylethan-
ones) with a variety of aliphatic aldehydes has been demon-
strated. By using 20 mol-% of unmodified cinchonine as cata-
lyst, the direct aldol reaction products were isolated in good
yields and with remarkably high
syn
diastereocontrol andgood asymmetric induction (40–78%
ee
). This newly elabo-
rated tertiary-amine-catalyzed direct asymmetric aldol reac-
tion has extended the scope of organocatalytic processes to
aromatic
α
-hydroxy ketones, which have hitherto been unre-
active towards enamine catalysis.