Abstract
The direct Michael addition of alkyl methyl ketones through the
acetyl methyl terminal to diethyl {[dimethyl(phenyl)silyl]methylene}malonate
was catalyzed by the (S )-N -(pyrrolidin-2-ylmethyl)pyrrolidine/trifluoroacetic
acid combination with high yield and excellent regio- and enantioselectivity.
The ketone adducts can easily undergo de-ethoxycarbonylation to
give β-silyl-δ-keto esters with excellent synthetic
potential. This has been demonstrated by the synthesis of a suitably
substituted β-silyl-δ-keto ester as an advanced
intermediate for a chiral hydroxylated pyrrolidine natural product,
(+)-preussin. Silicon-controlled diastereoselective reduction
of the ketone functionality of β-silyl-δ-keto
esters followed by lactonization of the resulting hydroxy esters
gave disubstituted δ-valerolactones. Advanced intermediates
for the antipodes of natural products, namely (+)-massoialactone
and (+)-mevinolin analogue, and natural products, namely
(-)-tetrahydrolipstatin and (+)-5-hexadecanolide,
have been achieved.
Key words
Michael addition - organosilicon compounds - methyl ketone - organocatalysis - regioselective - natural
product
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