Triphenylphosphine-Mediated Bifunctional Activation to Unlock Electrochemical Deoxygenative Thiolation of Alcohols

Herein, we report a metal-free electrochemical strategy for forming C-S bonds, which allowed us to obtain aryl, alkyl, allylic, and glycosyl thioethers using inexpensive alcohols as an electrophile and odorless disulfides as a sulfur source. The developed strategy fully eliminated the need for prefunctionalization of alcohols, thus showcasing a broad substrate scope, acceptable to excellent yields (52-93%), good functional group compatibility, and mild conditions. The key to the protocol is leveraging anodic oxidation, which drives PPh₃ to form alkoxyphosphonium intermediates, thereby activating the C-O bond of alcohols, while PPh₃ also reduces disulfides to generate RS^-.