Electroreductive thiocarboxylation of alkenes with cyclosulfonium salts and CO2: access to thioether acids

Abstract

Electroreductive carboxylation has emerged as a prominent strategy in modern organic synthesis, demonstrating well-established applications in two-component coupling reactions. However, multi-component reactions for selective mono-carboxylation remain underdeveloped with only a limited number of examples reported. We herein report a novel electroreductive intermolecular 1,2-thiocarboxylation of alkenes with cyclosulfonium salts and carbon dioxide (CO₂) via selective C–S bond cleavage for the construction of thioether acids. This transformation enables the single-step installation of both distal aryl thioether-functionalized alkyl chains and electrophiles into CC bonds of alkenes via a radical relay cascade mechanism, achieving sequential covalent bond formation through controlled radical insertion. With demonstrated broad substrate adaptability and excellent functional group tolerance, this method paves a straightforward and selective pathway for the modular synthesis of thiocarboxylation derivatives.