Photosensitized Synthesis of 1,2-Iminosulfides via β-Fragmentation of Bifunctional Oxime Reagents

The photosensitized 1,2-iminothiolation of olefins was achieved using bifunctional oxime ester reagents that simultaneously generate both thiyl and iminyl radicals. Central to reagent design was inclusion of an ethylene linker that facilitates rapid substrate synthesis, ensures that the stereoelectronic properties of the thiol do not impede photoactivation, and is liberated via β-fragmentation to produce thiyl radicals. Using this strategy, a range of thiols were engaged to generate valuable β-iminosulfide derivatives under mild organophotocatalysis.