Electrochemically induced oxidative rearrangement of alkylidenemalonates

Article abstract of DOI:10.1016/S0040-4020(98)00912-0

Alkylidenemalonates capable of double bond migration being electrolyzed in methanol or ethanol in the presence of alkali metal halides in an undivided cell equipped with Fe cathode are transformed into 2-alkyl-3,3- dimethoxyalkane-1,2-dicarboxylates in 70-90% yield via electrochemically induced oxidative rearrangement. Acidification of the reaction mixture after the electrolysis leads to the formation of 2-alkyl-3-oxoalkane-1,1- dicarboxylates. In the case of isobutylidenemalonate, the electrolysis intermediate dimethyl 3,3-dimethyl-2-methoxy-cyclopropane-1,1-dicarboxylate was isolated in 70% yield.