Direct C(sp³)-H functionalization with thiosulfonates via photoredox catalysis

While C(sp³)-S bonds exist in many biologically active compounds, the direct catalytic C(sp³)-H thiolation remains elusive. Herein, we report a convenient and green C(sp³)-H thiolation approach mediated by using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst. A wide range of C(sp³)-H bond-containing etheric, allylic, alkyl, ketonic, amidic substrates and sulfonyl-based SOMOphiles participated in the reaction, producing thioethers with high efficiency. The present protocol features green characteristics, such as being free of harmful oxidants and additives; step-economic; redox-neutral; and amenable to scale-up assisted by continuous-flow technology.