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.