Electrochemical Coupling of Biomass‐Derived Acids: New C8 Platforms for Renewable Polymers and Fuels

Electrolysis of biomass‐derived carbonyl compounds is an alternative to condensation chemistry for supplying products with chain length >C6 for biofuels and renewable materials production. Kolbe coupling of biomass‐derived levulinic acid is used to obtain 2,7‐octanedione, a new platform molecule only two low process‐intensity steps removed from raw biomass. Hydrogenation to 2,7‐octanediol provides a chiral secondary diol largely unknown to polymer chemistry, whereas intramolecular aldol condensation followed by hydrogenation yields branched cycloalkanes suitable for use as high‐octane, cellulosic gasoline. Analogous electrolysis of an itaconic acid‐derived methylsuccinic monoester yields a chiral 2,5‐dimethyladipic acid diester, another underutilized monomer owing to lack of availability. Electrolyzed biomass! Electrochemical coupling of biomass‐derived carboxylic acids is a viable alternative to aldol condensations for accessing >C6 carbon chain lengths from carbohydrates. Kolbe electrolysis of levulinic and itaconic acid derivatives leads to a C8 dione and branched diester, respectively, which are platforms for the production of biofuels and renewable monomers.