Selective Photoelectrochemical Oxidation of Vicinal Cyclohexanedicarboxylic Acids: A Mechanistic Study

Article abstract of DOI:10.1021/jo00288a035

The course of photooxidation of vicinal diacids on irradiated TiO2 suspensions proceeds via one-electron oxidative decarboxylation rather than two-electron oxidative bis-decarboxylation (which occurs on poised metal electrodes).The formation of a monocarboxylic acid as the major product indicates that trapping of an intermediate radical is competitive with further oxidation.The observed regiochemical preference in unsymmetrical diacids is rationalized by the conformational preference of the diacid adsorbed onto the photoactivated catalyst surface.