Concentrated Aqueous Peroxodicarbonate: Efficient Electrosyn‐ thesis and Use as Oxidizer in Epoxidations, S‐, and N‐Oxidations

Abstract

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.

Tuning Single-Atom Dopants on Manganese Oxide for Selective Electrocatalytic Cyclooctene Epoxidation

“…Several research groups have recently attempted olefin epoxidation via electrochemical methods. In situ electrochemical generation of chemical oxidants such as hydrogen peroxide, − active halogens, , or peroxodicarbonate were used to convert olefin substrates to their corresponding epoxides. Our group previously reported new electrochemical routes for olefin epoxidation, where sub-10-nm-sized manganese oxide nanoparticles catalyzed the direct epoxidation of cyclooctene using water as an oxygen atom source, with a faradaic efficiency of ∼30% .…”

Dehydrogenative Imination of Low-Valent Sulfur Compounds─Fast and Scalable Synthesis of Sulfilimines, Sulfinamidines, and Sulfinimidate Esters

“…We investigated electrochemically generated ex-cell oxygenation agents. Therefore, electrogenerated PODIC (peroxodicarbonate), a green and mild oxidizer, 59 was able to oxidize the sulfilimines in high to excellent yields with high selectivity ( Scheme 6 ). PODIC can be easily prepared from carbonate stock solutions using BDD anodes.…”

“…PODIC can be easily prepared from carbonate stock solutions using BDD anodes. The preparation can be performed either in homemade electrolyzers 59 or within commercially available setups, for example, from Condias. 60 For the oxygenation reaction, polar alcohols like MeOH and EtOH had been shown to work well as cost-efficient and sustainable solvents for this reaction.…”

Synthesis and Applications of Periodate for Fine Chemicals and Important Pharmaceuticals

“…The combination of a high-performance oxidizer generated by electrochemistry constitutes a perfect match. 22 Electrical current is a low-cost oxidizer and is environmentally benign if produced from renewable energy sources. 23 Conventional oxidants in turn extend the scope of reactivity and often provide higher selectivity.…”

“…Electrosynthesis is highly compatible and attractive with the expansion of renewable energies and is among the hottest topics in contemporary chemistry. − It allows a superior waste management and the development of sustainable as well as efficient chemical processes. The combination of a high-performance oxidizer generated by electrochemistry constitutes a perfect match . Electrical current is a low-cost oxidizer and is environmentally benign if produced from renewable energy sources .…”