Selective Degradation of Technically Relevant Lignin to Vanillic Acid and Protocatechuic Acid.

A new and practical method for the thermal degradation of technically relevant bio-based lignin is presented. By heating a solution of lignin in highly concentrated caustic potash, vanillic acid is almost exclusively obtained in yields up to 10.6 wt %. By altering the reaction parameters, the selectivity of the reaction can be shifted towards the demethylation product, protocatechuic acid, which is obtained in a yield of 6.9 wt %. Furthermore, the procedure was applicable to different types of Kraft and organosolv lignin. To create an economically feasible process, ion exchange resins were used for the work-up of the highly caustic reaction media without neutralizing the complete mixture. By the selective removal of the desired vanillic acid from the caustic potash, this alkaline media could directly be reused for at least 5 further lignin degradations without significant loss of yield.

Stereospecific Acylative Suzuki-Miyaura Cross-Coupling: General Access to Optically Active α-Aryl Carbonyl Compounds.

A novel strategy for the stereospecific Pd-catalyzed acylative cross-coupling of enantiomerically enriched alkylboron compounds has been developed. The protocol features an extremely high level of enantiospecificity to allow facile access to synthetically challenging and valuable chiral ketones and carboxylic acid derivatives. The use of a sterically encumbered and electron-rich phosphine ligand proved to be crucial for the success of the reaction. Furthermore, on the basis of experimental and computational studies, a unique mechanism for the transmetalation, assisted by the noncovalent interactions of the C(sp3)-based organoboron reagent, has been identified.