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Bifluoride Ion Mediated SuFEx Trifluoromethylation of Sulfonyl Fluorides and Iminosulfur Oxydifluorides.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-02-27 , DOI: 10.1002/anie.201813761 Christopher J Smedley 1 , Qinheng Zheng 2 , Bing Gao 2 , Suhua Li 3 , Andrew Molino 1 , Hendrika M Duivenvoorden 1 , Belinda S Parker 1 , David J D Wilson 1 , K Barry Sharpless 2 , John E Moses 1
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-02-27 , DOI: 10.1002/anie.201813761 Christopher J Smedley 1 , Qinheng Zheng 2 , Bing Gao 2 , Suhua Li 3 , Andrew Molino 1 , Hendrika M Duivenvoorden 1 , Belinda S Parker 1 , David J D Wilson 1 , K Barry Sharpless 2 , John E Moses 1
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SuFEx is a new‐generation click chemistry transformation that exploits the unique properties of S−F bonds and their ability to undergo near‐perfect reactions with nucleophiles. We report here the first SuFEx‐based procedure for the efficient synthesis of pharmaceutically important triflones and bis(trifluoromethyl)sulfur oxyimines from sulfonyl fluorides and iminosulfur oxydifluorides, respectively. The new process involves rapid S−F exchange with trifluoromethyltrimethylsilane (TMSCF3) upon activation by potassium bifluoride in anhydrous DMSO. The reaction tolerates a wide selection of substrates and proceeds under mild conditions without need for chromatographic purification. A tentative mechanism is proposed involving nucleophilic displacement of S−F by the trifluoromethyl anion via a five‐coordinate intermediate. The utility of late‐stage SuFEx trifluoromethylation is demonstrated through the synthesis and selective anticancer properties of a bis(trifluoromethyl)sulfur oxyimine.
中文翻译:
双氟化物离子介导的SuFEx三氟甲基化的磺酰氟和亚氨基氧二氟。
SuFEx是新一代点击化学转化,利用了S-F键的独特特性及其与亲核试剂进行近乎完美的反应的能力。我们在这里报告了第一个基于SuFEx的程序,可分别从磺酰氟和亚氨基硫代二氟化物有效合成药学上重要的三氟甲酮和双(三氟甲基)硫代亚氧肟酮。新工艺涉及与三氟甲基三甲基硅烷(TMSCF 3)的快速S-F交换)在无水DMSO中被氟化氢激活。该反应可耐受多种底物,并且可在温和条件下进行而无需色谱纯化。提出了一种试探性机制,涉及三氟甲基阴离子通过五配位中间体对S-F进行亲核取代。通过双(三氟甲基)硫氧亚胺的合成和选择性抗癌性能证明了后期SuFEx三氟甲基化的效用。
更新日期:2019-02-27
中文翻译:
![](https://scdn.x-mol.com/jcss/images/paperTranslation.png)
双氟化物离子介导的SuFEx三氟甲基化的磺酰氟和亚氨基氧二氟。
SuFEx是新一代点击化学转化,利用了S-F键的独特特性及其与亲核试剂进行近乎完美的反应的能力。我们在这里报告了第一个基于SuFEx的程序,可分别从磺酰氟和亚氨基硫代二氟化物有效合成药学上重要的三氟甲酮和双(三氟甲基)硫代亚氧肟酮。新工艺涉及与三氟甲基三甲基硅烷(TMSCF 3)的快速S-F交换)在无水DMSO中被氟化氢激活。该反应可耐受多种底物,并且可在温和条件下进行而无需色谱纯化。提出了一种试探性机制,涉及三氟甲基阴离子通过五配位中间体对S-F进行亲核取代。通过双(三氟甲基)硫氧亚胺的合成和选择性抗癌性能证明了后期SuFEx三氟甲基化的效用。