A stereoselective and electrocatalytic coupling reaction of isoeugenol has been reported for the first time in a 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)/boron-doped diamond (BDD) electrode system. This particular C-C bond formation and diastereoselectivity is driven by a solvate interaction between the radical species and another isoeugenol molecule. Due to an electrocatalytic cycle, only understoichiometric amounts of charge are necessary. Since electric current is directly employed as the oxidant, the reaction is metal and reagent-free. In addition, the electrolysis can be conducted in a very simple undivided beaker-type cell under constant current conditions. Therefore, the protocol is easy to use, suitable for scale-up, and inherently safe.

An electrochemical pinacol coupling reaction of acetophenone using a boron‐doped diamond (BDD) electrode has been reported. This transformation is driven by the one‐electron reduction of acetophenone on the BDD cathode, followed by an intermolecular radical coupling. Owing to the BDD's outstanding electrochemical properties, the pinacol‐type compound has been obtained in good conversion yield. The roles of a supporting electrolyte and solvent were addressed; (1) lithium ions contribute to increase in the reactivity of the radical intermediate. (2) Addition of water promotes the electron transfer process at the BDD surface. The reaction is relatively tolerant to para‐substituted acetophenone derivatives. Since electric current is directly employed as reducing reagents to generate a radical intermediate, the reaction is metal‐free, sustainable, and inherently safe.

Boron‐doped diamond (BDD) represents a powerful and innovative electrode material. In particular, in combination with fluorinated solvents such as 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP), the system exhibits the largest known electrochemical window of approximately 5 V in protic media. Furthermore, the anodic treatment allows the direct formation of oxyl radicals, which are known to exhibit specific reactivity. The electrochemical dehydrogenative phenol‐phenol cross‐coupling is a versatile and useful transformation to non‐symmetric biphenols. This electro‐organic conversion can be divided into two regimes: initial oxidation at the anode and the electrolyte‐controlled follow‐up reaction. This work intends to provide an answer about the influence of BDD electrodes on oxidation reactions in electrosynthesis. Depending on the electro‐organic transformation, the support material of BDD, its boron content, and its fabrication method have a significant influence on the electrosynthetic efficiency.