Anodic oxidation of substituted adamantanes

Abstract

Photoelectron spectra and voltammetric data are reported for a series of 1-alkyladamantanes. Anodic oxidation of the scries in either trifluoroacetic acid or acetonitrile gives charge-delocalised cation radicals. Whereas adamantane, 1-ethyladamantane. and 1-isopropyladamantane gave products by proton loss from the cation radical, other more highly substituted derivatives, e.g. 1-t-butyladamantane. give products preferentially by fragmentation of a carbon–carbon bond. Competition between deprotonation and fragmentation is controlled by the stability of the leaving carbocation; only if a tertiary group leaves is fragmentation dominant.