Synthesis and structural data of tetrabenzo[8]circulene

Robert W. Miller, Alexandra K. Duncan, Severin T. Schneebeli, Danielle L. Gray, Adam C. Whalley

Research output: Contribution to journalArticlepeer-review

Abstract

In 1976, the first attempted synthesis of the saddle-shaped molecule [8]circulene was reported. The next 37 years produced no advancement towards the construction of this complicated molecule. But remarkably, over the last six months, a flurry of progress has been made with two groups reporting independent and strikingly different strategies for the synthesis of [8]circulene derivatives. Herein, we present a third synthetic method, in which we target tetrabenzo[8]circulene. Our approach employs a Diels-Alder reaction and a palladium-catalyzed arylation reaction as the key steps. Despite calculations describing the instability of [8]circulene, coupled with the reported instability of synthesized derivatives of the parent molecule, the addition of four fused benzenoid rings around the periphery of the molecule provides a highly stable structure. This increased stability over the parent [8]circulene was predicted by using Clar's theory of aromatic sextets and is a result of the compound becoming fully benzenoid upon incorporation of these additional rings. The synthesized compound exhibits remarkable stability under ambient conditions - even at elevated temperatures - with no signs of decomposition over several months. The solid-state structure of this compound is significantly twisted compared to the calculated structure primarily as a result of crystal-packing forces in the solid state. Despite this contortion from the lowest-energy structure, a range of structural data is presented confirming the presence of localized aromaticity in this large polycyclic aromatic hydrocarbon.

Original languageEnglish (US)
Pages (from-to)3705-3711
Number of pages7
JournalChemistry - A European Journal
Volume20
Issue number13
DOIs
StatePublished - Mar 24 2014

Keywords

  • annulation
  • arenes
  • aromaticity
  • circulenes
  • fused-ring systems

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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