Peroxodicarbonates are of substantial interest as potentially powerful and sustainable oxidizers but have so far been accessible only in low concentrations with unsatisfactory energy efficiency. Concentrated (> 0.9 mol L À 1 ) peroxodicarbonate solutions have now been made accessible by the electrolysis of aqueous K 2 CO 3 / Na 2 CO 3 /KHCO 3 solutions at high current density of 3.33 A cm À 2 in an efficiently cooled circular flow reactor equipped with a boron-doped diamond anode and a stainless-steel cathode. Their synthetic potential as platform oxidizers was clearly demonstrated in transformations including sulfoxidation, N-oxidation, and epoxidation.

A simple and selective electrochemical synthesis by dehydrogenative coupling of unprotected 2,6‐ or 2,5‐substituted phenols to the desired 4,4′‐biphenols is reported. Using electricity as the oxidizing reagent avoids pre‐functionalization of the starting materials, since a selective activation of the substrates takes place. Without the necessity for metal‐catalysts or the use of stoichiometric reagents it is an economic and environmentally friendly transformation. The elaborated electrochemical protocol leads to a broad variety of the desired 4,4′‐biphenols in a very simplified manner compared to classical approaches. This is particular the case for the cross‐coupled products.

An emerging interest for the application of periodate in the synthesis of active pharmaceutical ingredients (APIs) and for the valorization of renewable feedstock is eminent. However, periodate exhibits a high molecular mass, is expensive compared to other common bulk-oxidizers and is used only reluctantly in technical applications. Recently, a new and green electrochemical synthesis was established. The preparation and regeneration method for periodate lowers costs and enables the use of periodate in the synthesis of regulated products. This review will briefly introduce the key innovations in the electrochemical synthesis of periodate and will survey the most important applications of periodate in the production of fine chemicals.

The N-oxidation of tertiary amines was achieved by using electrochemically generated peroxodicarbonate solutions as sustainable oxidizers. The presence of EDTA and 2,2,2-trifluoroacetophenone as a mediator was found to be crucial for converting water-insoluble substrates. Various tertiary amines were converted into their corresponding N-oxides in yields of up to 98%. The scope includes economically important surfactants and potential platform oxidizers.

Peroxodicarbonate represents a green and largely underexplored oxidizer generated electrochemically from aqueous carbonate solutions. Through state-of-the-art electrolyzer technology, highly concentrated solutions have now become accessible. These were successfully employed as green oxidizer in deborolative hydroxylations. A plethora of phenols and alcohols have thus been synthesized in up to 99 % from organoboron compounds using only green and non-toxic solvents. This transformation was successfully scaled-up to multi-gram batch sizes.