Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)-Based Planar Chiral Bent Cyclophanes by Rhodium-Catalyzed [2+2+2] Cycloaddition

Yukimasa Aida, Juntaro Nogami, Haruki Sugiyama, Hidehiro Uekusa, Ken Tanaka

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio- and enantioselective [2+2+2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bent p-terphenyl- and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of '99 % by diastereoselective 1,2-reduction. These 9-fluorenol-based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (gabs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increase as the tether length becomes shorter.

Original languageEnglish
Pages (from-to)12579-12588
Number of pages10
JournalChemistry - A European Journal
Volume26
Issue number55
DOIs
Publication statusPublished - 2020 Oct 1

Keywords

  • cycloadditions
  • enantioselective catalysis
  • planar chiral bent cyclophanes
  • polycyclic aromatic hydrocarbons
  • rhodium

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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