Effective Production of Selected Dioxolanes by Sequential Bio‐ and Chemocatalysis Enabled by Adapted Solvent Switching
Jan‐Dirk Spöring, Jan Wiesenthal, Victoria S. Pfennig, Jochem Gätgens, Kassem Beydoun, Carsten Bolm, Jürgen Klankermayer, Dörte Rother
Abstract
Abstract Most combinations of chemo‐ and biocatalysis take place in aqueous media or require a solvent change with complex intermediate processing. Using enzymes in the same organic solvent as the chemocatalyst eliminates this need. Here, it was shown that a complete chemoenzymatic cascade to form dioxolanes could be carried out in a purely organic environment. The result, including downstream processing, was compared with a classical mode, shifting solvent. First, a two‐step enzyme cascade starting from aliphatic aldehydes to chiral diols (3,4‐hexanediol and 4,5‐octanediol) was run either in an aqueous buffer or in the potentially biobased solvent cyclopentyl methyl ether. Subsequently, a ruthenium molecular catalyst enabled the conversion to dioxolanes [e. g., (4 S ,5 S )‐dipropyl‐1,3‐dioxolane]. Importantly, the total synthesis of this product was not only highly stereoselective but also based on the combination of biomass, CO 2 , and hydrogen, thus providing an important example of a bio‐hybrid chemical.