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DOI: 10.1055/a-1577-7972
Scholl Reaction of ortho-Phenylene-Bridged Cyclic Pyrrole-Thiophene Hybrid Hexamer
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 voltammetrySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1577-7972.
- Supporting Information
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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Reviews of oxidative fusion;
A fold-in approach was suggested to construct bowl-shaped aromatic compounds by designing a macrocyclic precursor containing the rim of the bowl followed by coupling to complete the central part of the bowl, see:
For reviews of hetero[8]circulenes, see:
Helicenophane: