Iron-Mediated One-Pot Dehydroxylative Cross-Electrophile Coupling of Alcohol with Disulfide for Thioether Synthesis by Using TCT as a Hydroxyl-Activating Agent

An efficient dehydroxythiolation between alcohols and disulfides using the widely abundant and cheapest iron as a reaction mediator was developed. The one-pot thiolation proceeded effectively via C-O bond activation with the aid of cyanuric chloride (TCT) as a hydroxyl-activating agent to give the corresponding thioethers in modest to excellent yields, displaying both a wide substrate scope (applicable to benzyl alcohol, allyl alcohol, and primary alkyl alcohol) and good functional group tolerance. In addition, diselenide was also proven to be an appropriate substrate for the protocol, and the reaction could be subjected to scale-up synthesis. Preliminary mechanistic examination revealed that transiently formed TCT-derived ether A, which is generated in situ via the reaction of TCT with alcohol, possibly serves as the pivotal intermediate of the cross-electrophile thioetherification.