Efficient Synthesis of Organosulfur Compounds via Electrochemical Biomass Conversion

Artificial C-S bond formation plays a pivotal role in the preparation of drugs and their intermediates. Utilizing an electrochemical method powered by renewable energy offers a sustainable pathway to produce organosulfur compounds, but challenged by the low faradic efficiency (<6.8%) and production rate (< 10 µmol cm-2 hr-1). In this study, we developed an efficient electrochemical approach to build C-S bonds and prepare a broad range of C-S species in high yield by coupling biomass oxidation with an S-containing nucleophile using commercial catalysts. Taking methanol as a representative, we successfully synthesized hydroxymethanesulfonate (HMS), sulfoacetate (SA), and methanesulfonate (MS). This system achieved a remarkable faradaic efficiency of over 95% within a low current density below 10 mA cm-2. At commercial current densities ranging from 100-1000 mA cm-2, the faradaic efficiency remained consistently over 60% in a practical flow reactor and high production rates, with stable operation over 50 hours without significant voltage increases or yield decreases at 100 mA cm-2. Four reaction pathways, with *CH2O, *CH3, and *CH2CH2O as key intermediates have been identified to facilitate the C-S bond formation. Impressively, this process can be effortlessly extended to synthesize a wide range of organosulfur and organonitrogen compounds from diverse feedstocks, achieving impressive production rates. Our approach promises to revolutionize the production of pharmaceuticals, textile chemicals, and agrochemicals.