Work

Flow electrooxidation of chiral alcohols with high enantioselectivity via integrated metal‐organic frameworks and aminoxyl radicals

Year: 2025

Type: article

Abstract: Chiral compounds play a pivotal role in pharmaceutical chemistry, and the oxidation of chiral alcohols to corresponding carboxylic acids is a crucial step. However, the enantioselectivity is susceptible to degradation due to sensitivity to enol isomerization and racemization. In this study, Ru/S‐Ni‐MOFs electrocatalysts with high specific surface area were synthesized. After undergoing electrochemical reconfiguration, which combined with 4‐acetamido‐TEMPO (ACT) as co‐catalysts to achieve efficient oxidation of chiral alcohols, with enantioselectivity reaching 99% at industrial‐grade current density of 500 mA/cm2. Additionally, 100 g of chiral acid were successfully synthesized with a yield of 98% and an enantioselectivity of 99% in the large‐scale electrolyzer. In situ experiments and theoretical calculations demonstrated that S doping shifts the center of d‐band toward the Fermi level, which stabilizes ACTH and inhibits the dissociation of OH, thereby enhancing electrocatalytic activity. This study presents an efficient synergistic electrocatalytic strategy for practical large‐scale electrosynthesis of chiral carboxylic acid compounds.

Source: AIChE Journal

DOI: 10.1002/aic.18847