Electrochemical Coupling of Biomass-Derived Acids: New C sub(8) Platforms for Renewable Polymers and Fuels

Electrolysis of biomass-derived carbonyl compounds is an alternative to condensation chemistry for supplying products with chain length >C sub(6) 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 >C sub(6) carbon chain lengths from carbohydrates. Kolbe electrolysis of levulinic and itaconic acid derivatives leads to a C sub(8) dione and branched diester, respectively, which are platforms for the production of biofuels and renewable monomers.