Electroreductive Desulfurative Transformations with Thioethers as Alkyl Radical Precursors

Herein, the use of aryl alkyl thioethers as precursors for C-centered alkyl radicals is demonstrated for desulfurative C-H and C-C bond formation under electroreductive conditions. The transformations occur with complete selectivity for C(sp3)-S bond cleavage, orthogonal to that of transition metal-catalyzed two-electron routes. Experimental and theoretical studies provide mechanistic insights that serve as a steppingstone for future use of thioethers as efficient radical precursors that can outcompete their established sulfone analogues.