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 (R2 S2 ). 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.

中文翻译：

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乙炔基苯并氧杂环酮试剂和硫醇的非常规反应性：范围和机制。

1,2-二硫-1-烯烃是具有生物活性的化合物，广泛应用于有机合成、功能材料、配位化学和制药领域。获取 1,2-二硫代-1-烯烃的传统方法通常需要过渡金属催化剂、专用或空气敏感配体、高温和二硫化物 (R2 S2 )。在此，提出了一种利用乙炔基苯并氧杂环酮 (EBX) 试剂和硫醇的通用且有效的策略，通过 EBX 和硫醇之间前所未有的反应性，形成具有优异区域选择性和立体选择性的 1,2-二硫-1-烯烃。这种操作简单的程序利用温和的条件，从而产生广泛的底物范围和高官能团耐受性。通过实验结果和 DFT 计算，观察到的意外反应性已得到合理化。