Unsymmetrical Oxidative Cleavage of Cyclic Ketones. Conversion to ω-Ethoxycarbonyl Aldoximes under Alkaline Conditions

Article abstract of DOI:10.1021/jo00002a040

A useful procedure for effecting the direct unsymmetrical cleavage of an enolizable ketone to an oximino ester has been developed.The process begins by deprotonation with LDA and is followed by the addition of ethyl nitrite in THF at low temperature.Rapid reaction customarily ensues with resultant overall nitrosolysis.Of particular importance is the facile application of this procedure to substrate ketones that are otherwise sensitive to acidic environments.This feature is exemplified in particular in the case of syn- and anti-sesquinorbornenones 34 and 35, access to which is described for the first time.Since the entire process is executed in a single flask, the methodology is very convenient to implement in practice.