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. 2025 Aug 6;16(35):15977-15981.
doi: 10.1039/d5sc03250d. eCollection 2025 Sep 10.

ThDP-dependent enzyme catalyzed oxidation of aldehydes

Xiaoyang Chen  1 , Meiting Zhou  1   2 , Xinyu Duan  3 , Yuting Zhang  1 , Xiaohe Chu  1 , Jian Xu  3
Affiliations

ThDP-dependent enzyme catalyzed oxidation of aldehydes

Xiaoyang Chen et al. Chem Sci. .

Abstract

Natural thiamine diphosphate (ThDP)-dependent enzymes are frequently utilized to catalyze the decarboxylation of β-keto acids and the benzoin condensation of aldehydes. Herein, we present a ThDP-dependent enzymatic oxidation of aldehydes mediated by sequential single electron transfer (SET) processes, utilizing hexachloroethane (C2Cl6) as the oxidant. The reaction exhibits high efficiency (yield up to 99% and turnover number up to 2000) and achieves effective stereoselective control for dynamic kinetic resolutions (e.e. up to 99%). This study uncovers a previously undiscovered capability of ThDP-dependent enzymes, thus broadening the functional repertoire of this enzyme class.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Oxidation of aldehydes to carboxylic acids. (a) Oxidation with hazardous oxidants. (b) ALDHs and NHCs catalyzed oxidation. (c) This work: ThDP-dependent enzymes catalyzed oxidation.
Fig. 2
Fig. 2. pfBAL catalyzed oxidation of 3a. (a) Optimization of the amount of C2Cl6. (b) Optimization of the reaction temperature. The yields and e.e. values were determined by GC.
Fig. 3
Fig. 3. (a) Mechanism experiments, (b) proposed mechanism, and (c) MD simulation of pfBAL with 3a; PDB: 3D7K.
See this image and copyright information in PMC

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