摘要

        由于磺酰氟分子在不同领域的广泛应用，寻找新的有效方法来获取磺酰氟化物具有相当大的研究意义。在这种情况下，氟化硫(VI)交换（SuFEx）点击化学正在成为最突出的此类方法之一。开发用于制备烷基磺酰氟的新型催化方法已成为有机合成中特别感兴趣的领域。与在芳基磺酰氟的合成方面已经取得的实质性进展相比，制备脂肪族磺酰氟化物的方法仍然较少探索。本文综述了烷基磺酰氟合成四种不同策略的最新进展：（i）光氧化还原催化，（ii）电催化，（iii）过渡金属催化，（iv）有机催化。这些反应产生不同的磺酰氟化物，这些氟化物可以作为生物活性分子和结构单元，适用于进一步的SuFEx转化。

 

介绍

       磺酰氟是化学合成的重要组成部分，在材料科学、化学生物学和药物发现中具有广泛的应用。1-3 从2014年开始，Sharpless及其同事证明，氟化硫(VI)交换（SuFEx）反应是一种新兴的点击反应，具有有机硫氟化物无与伦比的反应性和稳定性。4-6 由于叠氮化物和炔烃的连接能力以及温和铜催化的利用，第一代点击反应，即Huisgen叠氮-炔环加成反应已成为一种有用的工具。7-10 点击反应可以在耐水和耐氧条件下工作，从而产生出色的产物收率。与众所周知的磺酰氯相比，磺酰氟在酸性和碱性条件下更为稳定。11

 

        含硫(VI)化合物已广泛应用于制药12-15、 材料科学16和高分子科学17。磺酰氟在生物化学中的有趣应用包括抑制蛋白酶和作为生物探针（图1，（a）部分） 。18-20二芳基磺酰氟化物和二芳基硅烷基醚之间的SuFEx反应可生成聚磺酸盐-SuFEx聚合物，由于其高效性，在聚合物科学中具有独特的应用21-24。要合成所需的功能性分子，传统方法需要多步骤过程（图1，（b）部分）。此外，需要设计良好且易于获得的前驱体来应用催化过程。例如，乙烯磺酰氟（ESF，H2C=CHSO2F）已被引入作为制备各种氮基、氧基和碳基亲核试剂的良好迈克尔受体，可用于合成官能化烷基磺酰氟化物（图1，（c）部分）。25-27

 

        在这篇综述中，重点介绍了新的方法;包括光氧化还原催化、电催化、过渡金属催化和有机催化；已开发用于合成烷基磺酰氟化物（图1，（d）部分）。

图 1. (a)具有代表性的生物活性烷基磺酰氟的化学结构。 (b)用于合成烷基磺酰氟的传统方法。 (c) Sharpless千克级合成 ESF。 (d)本综述重点介绍的催化合成方法。

 

结论与展望

       我们研究了通过碳-碳或碳-杂原子键的形成及其与合适偶联剂的氟化物交换（SuFEx）反应合成烷基磺酰氟的过程。通过光氧化催化、电催化、过渡金属催化和有机催化，SO2F官能团的反应在活化后可获得多种碳水化合物和杂环。我们相信，这些方法将有助于扩大用于制药和农用化学品研究的含磺酰氟化合物库。

 

阿拉丁：https://www.aladdin-e.com

 

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