Sulfur (VI) Fluoride Exchange (SuFEx) via Glass–Assisted Organocatalysis

IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Advanced Synthesis & Catalysis Pub Date : 2024-11-06 DOI:10.1002/adsc.202401175
Ismat Nawaz, Maryam Nawaz, Rahman Shah Zaib Saleem, Ghayoor Abbas Chotana
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Abstract

An environmentally benign route for the synthesis of sulfonamides via Sulfur (VI) Fluoride Exchange (SuFEx) chemistry utilizing N-methylimidazole, that simultaneously act as a base, precatalyst, HF by-product scavenger, as well as solvent, is described. This one-step sulfonamide synthesis exhibits excellent reactivity toward highly electron-deficient and less nucleophilic anilines as well as aminopyridines while tolerating a wide range of functional groups. In addition to the desired sulfonamide target, we also isolated an ionic salt as the sole side product from the reaction mixture that has been identified as bis[1-methyl-1H-imidazole-3-ium] hexafluorosilicate (IV). The glass surface of reaction vessel is acting as the source of silicon present in the isolated side product. Formation of hexafluorosilicate salt is also facilitating the consumption of sulfonyl fluoride for sulfonamide synthesis. Optimization of the reaction under various conditions, as well as the isolation of the bis[1-methyl-1H-imidazole-3-ium] hexafluorosilicate (IV) salt, highlight the crucial role of N-methylimidazole and support the glass-assisted approach. Besides the first example of glass-assisted SuFEx catalyzed by benign organic bases, this reaction also offers an alternative route for accessing protic hexafluorosilicate-based molten salts without employing external HF. The synthetic utility of this SuFEx route for late-stage functionalization is also demonstrated.
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通过玻璃辅助有机催化实现硫 (VI) 氟化物交换 (SuFEx)
本研究介绍了一种利用 N-甲基咪唑同时作为碱、前催化剂、高频副产物清除剂和溶剂,通过硫(VI)氟化物交换(SuFEx)化学合成磺酰胺的无害环境路线。这种一步磺酰胺合成法对高度缺电子和亲核性较弱的苯胺以及氨基吡啶具有极佳的反应活性,同时可容忍多种官能团。除了所需的磺酰胺目标物外,我们还从反应混合物中分离出一种离子盐作为唯一的副产品,该副产品被鉴定为双[1-甲基-1H-咪唑-3-鎓]六氟硅酸盐 (IV)。反应容器的玻璃表面是分离副产物中硅的来源。六氟硅酸盐的形成还有助于消耗磺酰氟来合成磺酰胺。在各种条件下优化反应以及分离双[1-甲基-1H-咪唑-3-鎓]六氟硅酸盐 (IV) 突出了 N-甲基咪唑的关键作用,并支持玻璃辅助方法。该反应除了是首个由良性有机碱催化的玻璃辅助 SuFEx 实例外,还提供了一条无需外加 HF 即可获得原生六氟硅酸盐基熔盐的替代途径。此外,还展示了这种用于后期功能化的 SuFEx 路线的合成用途。
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来源期刊
Advanced Synthesis & Catalysis
Advanced Synthesis & Catalysis 化学-应用化学
CiteScore
9.40
自引率
7.40%
发文量
447
审稿时长
1.8 months
期刊介绍: Advanced Synthesis & Catalysis (ASC) is the leading primary journal in organic, organometallic, and applied chemistry. The high impact of ASC can be attributed to the unique focus of the journal, which publishes exciting new results from academic and industrial labs on efficient, practical, and environmentally friendly organic synthesis. While homogeneous, heterogeneous, organic, and enzyme catalysis are key technologies to achieve green synthesis, significant contributions to the same goal by synthesis design, reaction techniques, flow chemistry, and continuous processing, multiphase catalysis, green solvents, catalyst immobilization, and recycling, separation science, and process development are also featured in ASC. The Aims and Scope can be found in the Notice to Authors or on the first page of the table of contents in every issue.
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