Merging Iron Catalysis and Enzymatic Reduction: A Deracemization Strategy of Secondary Alcohols in Iron‐Based Deep Eutectic Solvents

The use of deep eutectic solvents (DESs) has gained increasing attention over the past two decades as green (co)solvents for performing organic reactions and biotransformations under mild conditions. In this study, we report a deracemization strategy that highlights the potential of FeCl 3 ·6H 2 O/urea (2:1 mol/mol) as a task‐specific DES. This neoteric solvent not only enhances substrate solubility but also plays a crucial role in the oxidation step of various racemic alcohols. The chemoenzymatic process consists of two consecutive sequential redox steps, starting with an initial non‐selective oxidation of the hydroxyl group using TEMPO in the FeCl 3 ·6H 2 O/urea medium, followed by a stereoselective bioreduction of the resulting carbonyl intermediate. Notably, the use of stereocomplementary alcohol dehydrogenases (ADHs)—namely ADH‐A (Prelog selectivity), Lb ADH, and evo 1.1.200 (anti‐Prelog selectivity)—is shown to be compatible with the DES system, enabling the efficient conversion of racemic alcohols into enantiomerically enriched products. Enantiomeric excesses of up to >99% were achieved, demonstrating the effectiveness of this DES‐based chemoenzymatic platform in producing optically active alcohols from racemic mixtures.