Unsymmetrical disulfides are widely found in the areas of food chemistry, pharmaceutical industry, chemical biology and polymer science. Due the importance of such disulfides in various fields, general methods for the nondirected intermolecular disulfuration of C-H bonds are highly desirable. In this work, the conversion of aliphatic C(sp³)-H bonds and aldehydic C(sp²)-H bonds into the corresponding C-SS bonds with tetrasulfides (RSSSSR) as radical disulfuration reagents is reported. The decatungstate anion ([W₁₀O₃₂]⁴⁻) as photocatalyst is used for C-radical generation via intermolecular hydrogen atom transfer in combination with cheap sodium persulfate (Na₂S₂O₈) as oxidant. Herein a series of valuable acyl alkyl disulfides, important precursors for the generation of RSS-anions, and unsymmetrical dialkyl disulfides are synthesized using this direct approach. To demonstrate the potential of the method for late-stage functionalization, approved drugs and natural products were successfully C-H functionalized.

不对称二硫化物广泛存在于食品化学、制药工业、化学生物学和高分子科学领域。由于此类二硫化物在各个领域的重要性，因此非常需要用于非定向分子间 CH 键二硫化的通用方法。在这项工作中，报告了将脂肪族 C(sp ³ )-H 键和醛类 C(sp ² )-H 键转化为相应的 C-SS 键与四硫化物 (RSSSSR) 作为自由基脱硫试剂。十钨酸根阴离子（[W ₁₀ O ₃₂ ] ^4-）作为光催化剂用于通过分子间氢原子转移与廉价的过硫酸钠（Na ₂ S ₂O ₈ ) 作为氧化剂。本文使用这种直接方法合成了一系列有价值的酰基烷基二硫化物、生成 RSS 阴离子的重要前体和不对称二烷基二硫化物。为了证明该方法在后期功能化方面的潜力，已批准的药物和天然产物成功地进行了 CH 功能化。