Evaluation of boron doped diamond electrodes for organic electrosynthesis on a preparative scale⋆

Abstract

We have investigated some anodic and cathodic transformations using boron doped diamond (BDD) electrodes. The oxidation of a propargylic alcohol as well as the aromatic side chain oxidation in water as electrolyte did not␣yield the desired products in high yield and selectivity and led mainly to the formation of CO2 due to␣electrochemical incineration of the starting material. With methanol as electrolyte, however, the reactivity of BDD electrodes is similar to graphite in most anodic methoxylation reactions, but the inactive behaviour of BDD electrodes leads to a different reaction pathway possibly involving methoxyl radicals with charge transfer from the electrolyte. It has been found that at BDD anodes benzylic single and double bonds can be split yielding aromatic acetals and esters. With phenanthrenes as starting material, o,o′-disubstituted biaryls were obtained. So the use of BDD electrodes provides an efficient and environmentally friendly access to this interesting class of compounds. The high H2 overpotential of BDD cathodes enables smooth and selective reduction of functional groups like oximes. Due to the high chemical and mechanical stability of the diamond layer of today’s electrodes, electrode lifetime as well as reproducibility of the electrosyntheses has improved markedly. Aqueous basic conditions, however, must be avoided for BDD anodes. These conditions result in degradation of the diamond surface.