Li Hengzhao, Peng Mengqi, Li Junyu, Wang Lijun, Do Hainam, Ni Ke, Wang Minlong, Yuan Zhankui, Zhao Tianxiao, Zhang Xiaohe, Zhang Xiaoxu, Hu Zhaonong, Ren Fazheng, An Jie
Key Laboratory of Precision Nutrition and Food Quality, Department of Nutrition and Health, China Agricultural University, Beijing, 100083, China.
College of Plant Protection, Northwest A&F University, Yangling, 712100, China.
Nat Commun. 2024 Sep 27;15(1):8325. doi: 10.1038/s41467-024-52606-w.
The dynamic disulfide linkage plays a vital role in various biological processes as well as drugs and biomaterials. The conversion of thiols to their corresponding disulfides is a hallmark of sulfur chemistry, but notoriously difficult to control. Achieving optimal reactivity and selectivity continues to pose significant challenges. Here, we describe a click chemistry for disulfide formation from thiols in both batch and flow-mode using SOF, which display exceptional selectivity toward disulfide formation through an effective nucleophilic substitution cascade. This reaction's unique characteristics satisfy the stringent click-criteria with its high thermodynamic driving force, straightforward conditions, wide scope, quantitative yields, exceptional chemoselectivity, and non-chromatographic purification process. The modular synthesis of symmetrical, unsymmetrical, cyclic and polydisulfides is demonstrated, along with the formation of disulfide cross-linked hydrogels.
动态二硫键在各种生物过程以及药物和生物材料中起着至关重要的作用。硫醇转化为相应的二硫化物是硫化学的一个标志，但众所周知难以控制。实现最佳的反应性和选择性仍然面临重大挑战。在这里，我们描述了一种使用SOF在间歇和流动模式下由硫醇形成二硫化物的点击化学方法，该方法通过有效的亲核取代级联反应对二硫化物的形成表现出非凡的选择性。该反应的独特特性以其高热力学驱动力、简单的条件、广泛的适用范围、定量产率、出色的化学选择性和非色谱纯化过程满足了严格的点击标准。展示了对称、不对称、环状和多二硫化物的模块化合成，以及二硫键交联水凝胶的形成。
