ThDP-dependent enzyme catalyzed oxidation of aldehydes.

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 (CCl) 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.