Dual gold and photoredox catalysis: visible light-mediated intermolecular atom transfer thiosulfonylation of alkenes† †Electronic supplementary information (ESI) available. CCDC 1494115 for 3n and 1494114 for 3s. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05093j Click here for additional data file. Click here for additional data file.

Regioselective difunctionalization of alkenes has attracted significant attention from synthetic chemists and has the advantage of introducing diverse functional groups into vicinal carbons of common alkene moieties in a single operation. Herein, we report an unprecedented intermolecular atom transfer thiosulfonylation reaction of alkenes by combining gold catalysis and visible-light photoredox catalysis. A trifluoromethylthio group (SCF3) and other functionalized thio groups together with a sulfonyl group were regioselectively introduced into alkenes in the most atom economical manner. A detailed mechanism study indicated that a synergistic combination of gold catalysis and photoredox catalysis is crucial for this reaction.