Methods enabling the broad diversification of C(sp3)–H bonds from a common intermediate are especially valuable in chemical synthesis. Herein, we report a site‐selective (N‐phenyltetrazole)thiolation of aliphatic and (hetero)benzylic C(sp3)–H bonds using a commercially available disulfide to access N‐phenyltetrazole thioethers. The thioether products are readily elaborated in diverse fragment couplings for C–C, C–O, or C–N construction. The C–H functionalization proceeds via a radical‐chain pathway involving hydrogen atom transfer by the electron‐poor N‐phenyltetrazolethiyl radical. Hexafluoroisopropanol was found to be essential to reactions involving aliphatic C(sp3)–H thiolation, with computational analysis consistent with dual hydrogen bonding of the N‐phenyltetrazolethiyl radical imparting increased radical electrophilicity to facilitate the hydrogen atom transfer. Substrate is limiting reagent in all cases, and the reaction displays an exceptional functional group tolerance well suited to applications in late‐stage diversification.

中文翻译：

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C(sp3)–H（N-苯基四唑）硫醇化作为分子多样化的工具

能够使常见中间体的 C(sp3)-H 键广泛多样化的方法在化学合成中特别有价值。在此，我们报告了使用市售二硫化物对脂肪族和（杂）苄基C（sp3）-H键进行位点选择性（N-苯基四唑）硫醇化以获得N-苯基四唑硫醚。硫醚产物很容易以 C-C、C-O 或 C-N 结构的不同片段偶联进行阐述。 C-H官能化通过自由基链途径进行，涉及缺电子的N-苯基四唑硫基自由基的氢原子转移。发现六氟异丙醇对于涉及脂肪族 C(sp3)-H 硫醇化的反应至关重要，计算分析与 N-苯基四唑硫基自由基的双氢键一致，增加了自由基的亲电性以促进氢原子转移。在所有情况下，底物都是限制性试剂，并且该反应表现出特殊的官能团耐受性，非常适合后期多样化的应用。