Electrocatalytic Vicinal Difunctionalization of Alkenes: Synchronous Construction of C–S and C–O Bonds

Sulfur-containing molecules are important in medicinal and biological chemistry, making their synthesis a central focus in organic chemistry. However, traditional methods often suffer from poor stability of sulfur bonds and a limited scope of oxygen nucleophiles. To address these challenges, we report a green, electrocatalytic strategy that employs nBu4NBr to generate bromine radicals in situ for the difunctionalization of alkenes. We achieved the first example of the selective, simultaneous construction of vicinal C–S and C–O bonds using diaryl disulfides and diverse oxygen nucleophiles. The reaction exhibits high atom economy, furnishing 53 products with yields up to 98%. This transition-metal-free and oxidant-free system proceeds under mild conditions with excellent functional-group tolerance and a broad substrate scope. Scale-up synthesis and control experiments demonstrate its practicality and reliability, highlighting its potential utility in complex molecule synthesis.