The direct modification of azole skeletons enables access to drug‐like molecules. The development of a highly compatible reaction platform for this pursuit still remains challenging. Herein, we report the use of sulfite as the single electron transfer (SET) reducing agent for the activation of functionalized bromoalkanes, elemental sulfur, and imidazoliniums for the transition metal‐free and base‐free N‐alkylation and thioketonization of azoles. Excellent functional group tolerance and high synthetic efficiency proved particularly advantageous for the rapid assembly of a large array of pharmaceutically‐oriented azole thiones, many of which contain synthetically and biologically useful functional groups. The direct transformation of drug molecules (such as Ketoconazole, Econazole, and Fluconazole) into their corresponding azole thiones has also been successfully achieved. Reactions with selenium also proceeded smoothly under the optimized conditions. Successful gram‐scale reactions demonstrate the good applicability of this methodology.

中文翻译：

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亚砜诱导的亚烷基N-烷基化和硫酮化使人们能够接触到各种亚砜亚砜

唑骨架的直接修饰使得能够接近类药物分子。为此目的，开发高度兼容的反应平台仍然具有挑战性。本文中，我们报道了亚硫酸盐作为单电子转移（SET）还原剂的用途，用于活化功能化的溴代烷烃，元素硫和咪唑啉鎓，以实现无过渡金属和无碱N的转化唑的烷基化和硫酮化。事实证明，出色的官能团耐受性和高合成效率对于快速组装大量的药用定向吡咯硫酮特别有利，其中许多含合成和生物学上有用的官能团。还成功地实现了药物分子（例如酮康唑，益康唑和氟康唑）直接转化为其相应的唑硫酮的转化。在最佳条件下，与硒的反应也顺利进行。成功的克级反应证明了该方法的良好适用性。