Hydroperoxides and Peroxides of Acetylene Derivatives

In this work, we develop a consistent set of oxygenated peroxy-hydrocarbon and acetylene-alcohol groups derived from the thermodynamic properties data of a set of hydroperoxides, peroxides, ethers and alcohols determined in previous chapters. 

Palladium(ii) complexes of trimethylsilyl enol ethers derived from ketones can be carbonylated (50 atm. CO) in the presence of an alcohol to give /S-keto-esters only three examples are quoted in this preliminary report. a, -Unsatur-ated esters can be converted into -keto-esters in ca. 70% yields using Na2PdCl4 in aqueous acetic acid containing t-butyl hydroperoxide or hydrogen peroxide. This method may be inappropriate if the starting ester contains other olefinic (and presumably acetylenic) bonds as these will probably also be attacked. 

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