Enantioselective Michael additions of cyclic beta -ketoesters to methyl vin
yl ketone catalyzed by cinchona alkaloids were studied. The results reveale
d that the induced enantioselectivity was significantly influenced by both
the structure of the catalyst and that of the substrate. Interesting differ
ences in the effect of the structure of the alkaloid on the enantioselectiv
ity of this reaction in the case of three beta -ketoesters were discovered.
High enantioselectivities were obtained in the reaction of ethyl 2-oxocycl
opentanecarboxylate and ethyl 2-oxocyclohexanecarboxylate (up to 83 and 80%
, respectively) at a low cinchona:reactant ratio of 1:500. As the specific
rotations of the product enantiomers, were unknown, they were determined by
optical rotation and chiral GC measurements and verified by NMR experiment
s. (C) 2001 Wiley-Liss, Inc.