The Kolbe or Non‐Kolbe electrolysis is one of the most studied electro‐organic reactions and a fundamental pillar of organic chemistry. In contrast to classical Kolbe dimerization of monocarboxylic acids, dicarboxylic acids are only scarcely subject for Kolbe electrolysis in the literature despite their vast natural abundance. Herein, we report on the intramolecular biradical recombination of dicarboxylic acids as a green way to prepare alkenes or alkynes over a newly proposed mechanistic route. Proceeding over a radical mechanism without dimerization, it clearly stands out from classical (Non‐)Kolbe electrolysis. In the presence of non‐toxic aqueous solvents, the desired products form in excellent yields (up to 83 %), which are the highest reported for this substrate class. Once feasibility had been shown for the electrolysis of methylsuccinic acid, we could demonstrate its application to a broad scope of different dicarboxylic acids.

Aiming at a circular carbon economy, electrosynthesis is gaining in importance. The conversion of bioderived materials using green electrons from renewable energy sources tackles challenges like fluctuating energy production and the integration into the already existing supply networks. Herein, we discuss concepts for transforming 150-year old Kolbe chemistry into flow processes. In a recirculation setup, levulinic acid is converted to the Kolbe product 2,7-octanedione with up to 75% yield. Single-pass setups allow for continuous production, for which conversion scales linearly with contact time. It was found that non-Kolbe electrolysis is even better suited toward continuous production because of the possibility to use lower substrate concentrations. We present an example of an n-alkyl acid converted using different flow cells including a 3D printed vessel for a semibatch non-Kolbe reaction. The electrochemically more challenging β-hydroxy-acid is selectively converted to a drop-in oxygenate fuel, increasing the hourly production compared to the batch process by five times.

The electrocatalytic reductive amination offers a green pathway to N-containing platform and fine chemicals by using water as a hydrogen source and benign reaction conditions.

In the renaissance of organic electrochemistry, 150‐year‐old Kolbe chemistry offers a sustainable pathway to liquid energy carriers and commodities. Herein, easy‐access design methods for electrochemical microreactors employing 3D printing and simple post processing techniques are presented. The continuous Non‐Kolbe electrolysis of monomethyl succinic acid is studied as a test reaction for the production of an industrially relevant, green monomer. In a semi‐batch setup, methyl acrylate is produced with a maximum yield of 34 %, similar to results from a thoroughly optimized batch reaction in a prior study. In single‐pass experiments, a comparable faradaic efficiency of 54 % is achieved.

This study elucidates key parameters allowing the electrochemical valorization of cellobiose, by creating value-added products by both, anodic oxidation, and cathodic reduction. We demonstrate the first electrochemical reduction of cellobiose to cellobitol in a divided cell using Pb as cathode, leading up to 49 % conversion, though with long reaction times (over 26 h) and low coulombic efficiency (CE) of 4 %. The successful synthesis of cellobionic acid was demonstrated by mediated oxidation in an undivided electrochemical cell, using a graphite anode and CaBr 2 as electrocatalytic mediator. Cellobiose oxidation was highly selective, allowing for up to 92 % conversion to cellobionic acid at 48 % CE when using a charge of 2 FE.