Unconventional Reactivity of Ethynylbenziodoxolone Reagents and Thiols: Scope and Mechanism

1,2-Dithio-1-alkenes are biologically active compounds widely implemented throughout organic synthesis, functional materials, coordination chemistry, and pharmaceuticals. Traditional methods for accessing 1,2-dithio-1-alkenes often demand transition metal catalysts, specialized or air-sensitive ligands, high temperatures, and disulfides (R₂S₂). Herein, a general and efficient strategy utilizing ethynylbenziodoxolone (EBX) reagents and thiols is presented that results in the formation of 1,2-dithio-1-alkenes with excellent regioselectivity and stereoselectivity through unprecedented reactivity between the EBX and the thiol. This operationally simple procedure utilizes mild conditions, which result in a broad substrate scope and high functional-group tolerance. The observed unexpected reactivity has been rationalized through both experimental results and DFT calculations.