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TfOH-Promoted Reactions of TMS-Ethers of CF3–Pentenynoles with Arenes. Synthesis of CF3-Substituted Pentenynes, Indenes, and Other Carbocyclic Structures
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-12-29 , DOI: 10.1021/acs.joc.0c02361 Aleksey V Zerov 1 , Irina A Boyarskaya 1 , Olesya V Khoroshilova 1 , Irina N Lavrentieva 2 , Alexander V Slita 2 , Ekaterina O Sinegubova 2 , Vladimir V Zarubaev 2 , Aleksander V Vasilyev 1, 3
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-12-29 , DOI: 10.1021/acs.joc.0c02361 Aleksey V Zerov 1 , Irina A Boyarskaya 1 , Olesya V Khoroshilova 1 , Irina N Lavrentieva 2 , Alexander V Slita 2 , Ekaterina O Sinegubova 2 , Vladimir V Zarubaev 2 , Aleksander V Vasilyev 1, 3
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Trimethylsilyl ethers of 1,5-diaryl-3-(trifluoromethyl)-pent-1-en-4-yn-3-oles [Ar–C≡C–C(CF3)(OSiMe3)–CH═CH–Ar′] in the superacid TfOH give rise to reactive conjugated CF3-allylic-propargylic cations [Ar–C≡C–C+(CF3)–CH═CH–Ar′]. These species react with arenes in the presence of 1.5 equiv of TfOH forming regio- and stereoselectively E-1,1,5-triaryl-3-(trifluoromethyl)-pent-2-en-4-ynes [Ar–C≡C–C(CF3)═CH–CHAr′(Ar″)] in good yields. In the excess of TfOH, these CF3-pentenynes are further intramolecularly cyclized into CF3-bicyclic dihydroanthracene derivatives (“helicopter”-like molecules). The CF3-pentenynes may also react with arenes, as external nucleophiles, leading to CF3-indenes. These two main reaction pathways depend on internal nucleophilicity of aryl substituents in CF3-pentenynes and external nucleophilicity of aromatic molecules. Plausible cationic reaction mechanisms have been discussed. CF3-bicyclic dihydroanthracene derivatives have been studied regarding their cytotoxicity and virus-inhibiting activity against influenza virus A/Puerto Rico/8/34 (H1N1) in MDCK cell line.
中文翻译：
TfOH促进CF 3-戊炔醇的TMS醚与芳烃的反应。CF 3取代的戊烯，茚基和其他碳环结构的合成
1,5-二芳基-3-（三氟甲基）-pent-1-en-4-yn-3-oles [Ar–C≡C–C（CF 3）（OSiMe 3）–CH═CH–Ar的三甲基甲硅烷基醚']在超强酸TfOH中产生反应性共轭CF 3-烯丙基-炔丙基阳离子[Ar–C≡CC–C +（CF 3）–CH═CH–Ar']。这些物质在1.5当量的TfOH存在下与芳烃反应，形成区域选择性和立体选择性的E- 1,1,5-三芳基-3-（三氟甲基）-戊-2-烯-4-炔[Ar–C≡C– C（CF 3）═CH–CHAr'（Ar''）]，收率高。在过量的TfOH中，这些CF 3-戊烯炔进一步分子内环化为CF 3-双环二氢蒽衍生物（“直升机”样分子）。CF 3-戊烯也可以作为外部亲核试剂与芳烃反应，生成CF 3-茚。这两个主要反应途径取决于CF 3-戊烯炔中芳基取代基的内部亲核性和芳族分子的外部亲核性。已经讨论了合理的阳离子反应机理。已经研究了CF 3-双环二氢蒽衍生物在MDCK细胞系中对流感病毒A /波多黎各/ 8/34（H1N1）的细胞毒性和病毒抑制活性。
更新日期：2021-01-16
中文翻译：
TfOH促进CF 3-戊炔醇的TMS醚与芳烃的反应。CF 3取代的戊烯，茚基和其他碳环结构的合成
1,5-二芳基-3-（三氟甲基）-pent-1-en-4-yn-3-oles [Ar–C≡C–C（CF 3）（OSiMe 3）–CH═CH–Ar的三甲基甲硅烷基醚']在超强酸TfOH中产生反应性共轭CF 3-烯丙基-炔丙基阳离子[Ar–C≡CC–C +（CF 3）–CH═CH–Ar']。这些物质在1.5当量的TfOH存在下与芳烃反应，形成区域选择性和立体选择性的E- 1,1,5-三芳基-3-（三氟甲基）-戊-2-烯-4-炔[Ar–C≡C– C（CF 3）═CH–CHAr'（Ar''）]，收率高。在过量的TfOH中，这些CF 3-戊烯炔进一步分子内环化为CF 3-双环二氢蒽衍生物（“直升机”样分子）。CF 3-戊烯也可以作为外部亲核试剂与芳烃反应，生成CF 3-茚。这两个主要反应途径取决于CF 3-戊烯炔中芳基取代基的内部亲核性和芳族分子的外部亲核性。已经讨论了合理的阳离子反应机理。已经研究了CF 3-双环二氢蒽衍生物在MDCK细胞系中对流感病毒A /波多黎各/ 8/34（H1N1）的细胞毒性和病毒抑制活性。
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