Electrochemically driven deoxychlorination of aliphatic alcohols via alkoxysulfonium intermediates.

Native aliphatic alcohols are highly abundant feedstocks for organic synthesis but remain challenging as alkyl donors. Herein, a new class of electrochemically triggered deoxygenative substitution of aliphatic alcohols is described. In the presence of diphenyl sulfide, the protocol furnishes alkyl chloride products under mild conditions and tolerates functional groups such as amines, carbamates, heteroaromatic rings, sulfones and free carboxylic acids. Mechanistic studies indicate that the reaction proceeds via nucleophilic substitution of alkoxysulfonium intermediates with inversion of configuration at the hydroxyl carbon, representing a new avenue for deoxyfunctionalization of aliphatic alcohols under electrochemical conditions.