Gamma-carbon-alkylation of a �-dicarbonyl compound is most commonly accomplished by trapping the preformed dianion of a �-dicarbonyl compound with an electrophile such as an aldehyde.  Traditionally, highly reactive bases such as lithium diisopropylamide, sodium hydride, and n-butyl lithium have been used for this transformation.  We have found that equilibrating bases such as carbonates and alkoxides can be used in place of these strong bases for gamma-carbon-alkylation resulting in the formation of d-lactones from �-ketoesters and enone-amides from �-ketoamides when an alcohol solvent is used.  In addition, hydroxyketoesters can be prepared from the salt of a �-ketoester when an ether solvent is used.  This discovery provides a simple and greener alternative for performing regioselective alkylations of �-dicarbonyl compounds.

Gamma-carbon-alkylation of �-dicarbonyl compounds using equilibrating conditions

246th National Meeting (2013)

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