Bioinspired Lanthanide-<i>ortho</i>-Quinone-Catalyzed Aerobic Disulfide Formation

The oxidation of thiols to form disulfide bonds is a crucial reaction in biological systems. Inspired by methanol dehydrogenase (MDH), we developed a bioinspired quinone-catalyzed aerobic oxidation reaction for thiol oxidation to disulfides. Based on mechanistic studies, we have confirmed that a semiquinone radical anion, coordinated by a lanthanum ion, serves as the critical intermediate. The thiol-quinone redox shuttle was further shown to mediate the MDH-like activity in the aerobic oxidation of alcohols.