eCarbonyls: an electrochemical thioether mediated oxidation of alcohols to aldehydes and ketones

We report eCarbonyls, a scalable, metal-free electrochemical oxidation of alcohols that mimics key features of the classical Swern reaction while avoiding its reliance on cryogenic conditions and hazardous reagents. Operating at room temperature in an undivided cell, this process employs a stable thioether mediator to generate reactive radical cation intermediates that enable selective oxidation of primary and secondary alcohols to aldehydes and ketones. The method displays broad substrate scope, with up to 98% isolated yields across more than 25 examples, and excellent tolerance toward sensitive functional groups, including azides, boronates, and silyl ethers. Mechanistic studies confirm the role of anodically generated thioether radical cations and highlight the importance of the external base. Notably, eCarbonyls is readily scalable and adaptable to flow electrolysis, enabling multigram synthesis and offering a safe, sustainable platform for academic and industrial applications.