Electrochemical synthesis on boron-doped diamond

Boron-doped diamond (BDD) is a novel and innovative electrode material. In protic media and particular aqueous electrolytes BDD exhibits a large over potential for the evolution of molecular hydrogen and oxygen. The large chemical window allows a variety of electrochemical conversions to be conducted. The anodic process treatment generates oxyl species directly which are known to be extremely reactive. Usually, the electrochemical mineralization of the organic components in the electrolyte occurs. However, with control of the reactivity of these intermediates the use in electroorganic synthesis can be realized. Until today mostly anodic conversions have been studied at BDD. Since hydroxyl radicals can be efficiently formed and exhibit an enormous oxidative power they are exploited for the electroorganic synthesis. In general, two strategies can be applied to circumvent electrochemical incineration: First, the substrate serves as solvent and partial conversion exploits statistics to gain selectivity for the desired product. This particular approach is useful when the excess of substrate can subsequently be evaporated, and is readily available and inexpensive. The second strategy uses fluorinated alcohols as additives which enlarge the chemical window. The specific role of these fluorinated solvents can be attributed to the stabilization of hydroxyl or methoxyl radicals by supramolecular taming of these intermediates. Moreover, these additives paved the way to the first anodic phenol-arene cross-coupling reaction. (C) 2012 Elsevier Ltd. All rights reserved.