TfOH-promoted reactions of TMS-ethers of CF3−pentenynoles with arenes. Synthesis of CF3-substituted pentenynes, indenes, and other carbocyclic structures

Aleksander V. Vasilyev, Aleksey V. Zerov, Irina A. Boyarskaya, Olesya V. Khoroshilova, Irina N. Lavrentieva, Alexander V. Slita, Ekaterina O. Sinegubova, Vladimir V. Zarubaev

Research outputpeer-review

Abstract

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.

Original languageEnglish
JournalJournal of Organic Chemistry
DOIs
Publication statusAccepted/In press - 2021

Scopus subject areas

  • Organic Chemistry

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