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Synthesis 2022; 54(01): 147-152
DOI: 10.1055/a-1577-7972
paper

Scholl Reaction of ortho-Phenylene-Bridged Cyclic Pyrrole-Thiophene Hybrid Hexamer

Yusuke Matsuo
,
Atsuhiro Osuka
,
Takayuki Tanaka  ∗
This work was supported by Grants-in-Aid from the JSPS KAKENHI (JP20K05436). Y.M. gratefully acknowledges a JSPS Research Fellowship for Young Scientists.
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Abstract

The Scholl reaction of ortho-phenylene-bridged cyclic pyrrole-thiophene hybrid hexamer gave cyclophane-type [5]heterohelicene exclusively in 45% yield. The structure was unambiguously revealed by X-ray diffraction analysis. This helicenophane-type compound showed sharp absorption and fluorescence spectra, reflecting its rigid structure. The reaction path was analyzed on the basis of DFT calculations, and it was found that the formation of the [5]helicene-dimer is thermodynamically favored and further oxidation is prohibited due to the increased strain energy.

Key words

intramolecular oxidative coupling - cyclophane - helicene - homodesmotic reaction - fluorescence - cyclic voltammetry

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1577-7972.
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Publication History

Received: 02 July 2021

Accepted after revision: 03 August 2021

Accepted Manuscript online:
03 August 2021

Article published online:
27 August 2021

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