Oxymetallation. Part III. Competitive epoxidation during the hydridodemercuration of β-mercurated dialkyl peroxides with sodium borohydride

Abstract

Reduction by sodium borohydride of the compounds R¹R²C(OOBu^t) CH₂·HgX, which are formed by t-butyl-peroxymercuration of terminal alkenes, leads to the formation of epoxides, R¹R²[graphic omitted], in addition to the expected dialkyl peroxides, R¹R²C(OOBu^t)Me. The amount of epoxidation increases with increasing alkylation in the terminal alkene and with the temperature at which the reduction is carried out. It is suggested that the results are consistent with homolytic cleavage of the carbon-mercury bond during demercuration.