Deep Eutectic Solvents as Media in Alcohol Dehydrogenase‐Catalyzed Reductions of Halogenated Ketones

Abstract The application of deep eutectic solvents (DESs) in biotechnological processes has gained an outstanding relevance, as they can be used as greener media to obtain higher productivities and selectivities. In the present contribution, an eutectic mixture composed of choline chloride (ChCl): glycerol (1 : 2 mol/mol) has been used as a reaction medium in combination with Tris−SO 4 50 mM buffer pH 7.5, applied to the alcohol dehydrogenase (ADH)‐catalyzed reduction of various carbonyl precursors of chiral halohydrins. These alcohols are key intermediates of biologically active compounds, and hence they are of industrial interest. In the presence of up to 50 % v/v of DES, these biotransformations were achieved up to 300–400 mM of the α‐halogenated ketone substrate, getting access to the final compounds with excellent conversions (usually >90 %) and enantiomeric excess ( ee >99 %). Among the different ADHs tested, two stereocomplementary enzymes ( Lactobacillus brevis ADH and Rhodococcus ruber ADH) afforded the best results, so both alcohol enantiomers could be obtained in all the studied examples. Selected bioreductions were scaled up to 250 mg and 1 g, demonstrating the potential that DESs can offer as media in redox processes for substrates with low solubility in water.