Electro‐Oxidative Alkoxylation‐Thiolation of Vinyl Ethers

An electro‐oxidative protocol for the alkoxylation‐thiolation of vinyl ethers is developed, employing nonvolatile diaryl disulfides as atom‐economical arylthio sources under oxidant‐free and metal‐free conditions. 4‐(Trifluoromethyl)pyridine is used as a base additive to suppress side reactions and improve the yield. A wide range of substrates with diverse structures and functional groups are compatible with this protocol. Mechanism experiments show that the reaction involves a mechanism in which an arylthio radical is generated at the anode as the key intermediate.