Electrochemical generation of storable organic oxidants for use in sustainable catalytic transformations

• Applicant: Professor Dr. Lukas J. Gooßen
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2019
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 413163866

The successful development of a circular flow electrolyzer, which dissipates the heat generated during the anodic process with such efficiency that even sensitive oxidizers can be produced in previously elusive concentrations, has opened up a wealth of opportunities for the second funding period. Highly concentrated peroxodicarbonate solutions have been shown to be potent oxidizers, but the unsatisfactory miscibility of potassium peroxodicarbonate with organic reagents and the high solubility of the oxidation product in the aqueous phase are key obstacles preventing further progress. These will be tackled in the second funding period. Our first goal is to electrogenerate oxidizers that are better miscible with organic substrates. In this context, we will target ionic liquids containing peroxodicarbonate anions. In a second project, we will investigate if our reactor allows to access more lipophilic oxidizers, such as peracids, peranhydrides, persulfates or hypervalent iodine components as well as ozone. We will identify potential applications for these electrochemically generated oxidizers, including N-oxidation of amines, anilines, ammonia or even of dinitrogen, as well as alkene epoxidations, Baeyer-Villiger oxidations etc. We will finally combine the electrochemical generation of the oxidants with ex-cell oxidations within a two-chamber loop reactor. The electrochemically generated oxidant will be mixed with an organic phase containing a lipophilic substrate. After phase separation, the aqueous phase will be continuously funneled back into the electrochemical flow cell, while the organic product phase will be separated off. As the first model reaction, we will use the synthesis of commercially meaningful N-dodecyl-N,N-dimethylamine N-oxide.

• DFG Programme: Research Units
• Subproject of: FOR 2982: UNODE - Unusual Anode Reactions