Cyclohexene oxide anodic oxidation

In contrast to other cleavage reagents, this anodic oxidation does not show stereochemical preference. In addition, ether derivatives are oxidized in similar current efficiencies to those of the parent 1,2-diols. Cyclohexene oxide is oxidized via the corresponding hydroxy edier. 

When a palladium(II)-hydroquinone system is used as the mediator4 in the anodic oxidation of 1,3-cyclohexadiene in acetic acid, either trans- or cis- 1,4-diacetoxy-2-cyclohexene is formed with rather high selectivity, though the possible formation of 1,2-diacetoxylated compound is not discussed. 

This mode of anodic addition is so far limited to halogens. Cpe of cyclohexene in acetonitrile - Et4N+Cl at the oxidation potential of the chloride ion yields 80% 1 -cliloro-2-acetamidocyclohexane21 ° whose formation is rationalized by electrophilic addition of anodically generated chlorine to the double bond and... 

In general, the anodic oxidation of simple alkenes in nucleophilic solvents yields products resulting from both allylic substitution and oxidative addition of nucleophiles. Cyclohexene has been studied extensively as starting compound. The anodic oxidation of cyclohexene in methanol or acetic acid... 

The reaction can also be performed by anodic oxidation of cyclohexene/chloride ion mixtures in acetonitrile, tra .v-l-acctvlamino-2-chlorocyclohcxanc was obtained in 80% yield44-183-184. 

The anodic dimethoxylation of simple cyclic olefins, such as cyclohexenes, results in the predominant formation of ra/w-dimethoxycyclohexanes [303,305]. However, Barba and CO workers [306] reported that the stereochemistry of l,2-dimethoxy-l,2-dihydroace-naphthene derived from acenaphthene is drastically influenced by the anode material. Palasz and Utley [307] have reported that jV-acetylpiperidines are methoxylated via the enamide intermediate species formed by the oxidation. 1,3-Dienes are also 1,4-dimethoxylated in low stereoselectivity [293]. The anodic methoxylation of or-pinene proceeds similarly to the acetoxylation, resulting in the formation of two sets of stereoisomeric products [308]. 

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