Photoinduced Alkene Carbothiolation via Fe/Ni Dual Catalysis

Alkene carbothiolation enables simultaneous construction of C–C and C–S bonds yet remains challenging for the synthesis of thioethers because low-valent sulfur species readily coordinate to and deactivate transition metal catalysts. Herein, we report a photoinduced Fe/Ni dual-catalytic system that achieves alkene carbothiolation through direct C(sp 3 )–H activation of simple alkanes. From the merger of ligand-to-metal charge transfer (LMCT)-enabled alkyl radical generation with nickel-catalyzed cross-coupling/sulfide oxidation state modulation, this strategy enables efficient installation of both carbon and sulfur functionalities across alkenes while bypassing the need for prefunctionalized radical precursors. The method provides straightforward access to structurally diverse thioethers from abundant hydrocarbon feedstocks and exhibits broad functional group tolerance and good scalability.