Fluorinated and trifluoromethylated corannulenes

Bernd M. Schmidt, Berit Topolinski, Mihoko Yamada, Shuhei Higashibayashi, Mitsuhiko Shionoya, Hidehiro Sakurai, Dieter Lentz

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The syntheses and properties of corannulenes carrying electron-withdrawing groups (F, CF3, C6F5) are reported. Direct fluorination of corannulene (C20H10) was carried out with xenon difluoride, and the crystal structure of the product was confirmed by the X-ray analysis. Novel trifluoromethylated corannulenes, including the versatile 4,9-dibromo-1,2-bis(trifluoromethyl)corannulene, were obtained by various established ring-closing reactions. Besides the use of hexafluorobutyne for the construction of fluoranthenes by Diels-Alder reaction as precursor molecules to form 1,2-disubstituted corannulenes, bis(pentafluorophenyl)acetylene was employed as dienophile. The molecular structure and crystal packing of a trifluoromethylated corannulene was determined by single-crystal X-ray analysis and compared with those known brominated and trifluoromethylated corannulenes. The general electron-acceptor properties of corannulenes bearing substituents introduced in particular positions by liquid-phase synthesis are discussed together with published computational results. Stacked bowls: Starting from substituted fluoranthenes, novel corannulenes bearing electron-withdrawing groups were synthesized regioselectively. Moreover, the first fluorinated corannulene was synthesized by direct fluorination. Crystallographically studied trifluoromethylated corannulenes showed desirable π-stacked structures (see figure), despite their electron-acceptor strength in solution.

Original languageEnglish
Pages (from-to)13872-13880
Number of pages9
JournalChemistry - A European Journal
Volume19
Issue number41
DOIs
Publication statusPublished - 2013 Oct 4
Externally publishedYes

Keywords

  • corannulenes
  • electrochemistry
  • fluorine
  • stacking interactions
  • trifluoromethylation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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  • Cite this

    Schmidt, B. M., Topolinski, B., Yamada, M., Higashibayashi, S., Shionoya, M., Sakurai, H., & Lentz, D. (2013). Fluorinated and trifluoromethylated corannulenes. Chemistry - A European Journal, 19(41), 13872-13880. https://doi.org/10.1002/chem.201301910