Exploration of New Biomass‐Derived Solvents: Application to Carboxylation Reactions

A range of hitherto unexplored biomass‐derived chemicals have been evaluated as new sustainable solvents for a large variety of CO(2)‐based carboxylation reactions. Known biomass‐derived solvents (biosolvents) are also included in the study and the results are compared with commonly used solvents for the reactions. Biosolvents can be efficiently applied in a variety of carboxylation reactions, such as Cu‐catalyzed carboxylation of organoboranes and organoboronates, metal‐catalyzed hydrocarboxylation, borocarboxylation, and other related reactions. For many of these reactions, the use of biosolvents provides comparable or better yields than the commonly used solvents. The best biosolvents identified are the so far unexplored candidates isosorbide dimethyl ether, acetaldehyde diethyl acetal, rose oxide, and eucalyptol, alongside the known biosolvent 2‐methyltetrahydrofuran. This strategy was used for the synthesis of the commercial drugs Fenoprofen and Flurbiprofen.