Lional Natassa, Miloserdov Fedor M, Zuilhof Han
Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, Wageningen, 6708 WE, The Netherlands.
School of Pharmaceutical Science & Technology, Tianjin University, 92 Weijin Road, Nankai District, Tianjin, 300072, China.
Angew Chem Int Ed Engl. 2024 Sep 2;63(36):e202406915. doi: 10.1002/anie.202406915. Epub 2024 Jul 29.
S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF gas. Safety issues and inaccessibility of SOF strongly hamper the developments of these organic compounds. Here we describe the synthesis and applications of 2-methylimidazole-1-(N-tert-octyl)sulfonimidoyl fluoride (ImSF), a novel bench-stable analogue of SOF. ImSF is synthesized on a gram scale via a double fluorination of t-OctNSO. We show ImSF can undergo substitution reactions with phenols and amines, which lead to sulfurimidates and sulfuramidimidates, respectively, the intrinsically chiral analogous of medicinally relevant sulfates and sulfamates in which an S=O moiety is replaced by S=NR unit. Finally we demonstrate that such substitutions can occur enantiospecifically, providing the first entry to chiral sulfurimidates and sulfuramidimidates.
具有多个氮或氧取代基的S(VI)化合物通常难以制备，一些关键路线，如多模式硫(VI)氟交换（SuFEx）化学，依赖于非常有用但具有危险性的SOF气体。SOF的安全问题和难以获取性严重阻碍了这些有机化合物的发展。在此，我们描述了2-甲基咪唑-1-(N-叔辛基)磺酰亚胺氟化物（ImSF）的合成与应用，它是一种新型的、在实验室条件下稳定的SOF类似物。ImSF通过叔辛基NSO的双氟化反应以克级规模合成。我们表明，ImSF能与酚类和胺类发生取代反应，分别生成硫亚胺酯和硫酰胺亚胺酯，它们是医学上相关的硫酸盐和磺酸盐的固有手性类似物，其中S=O部分被S=NR单元取代。最后，我们证明这种取代反应可以对映体特异性地发生，为手性硫亚胺酯和硫酰胺亚胺酯的合成提供了首个方法。
