We demonstrate a new synthetic strategy to cyclophanes containing thiophene and indole moieties via Grignard addition, Fischer indolization and ring-closing metathesis as key steps.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4578400PMC
http://dx.doi.org/10.3762/bjoc.11.165DOI Listing

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Article Synopsis
  • The study focuses on creating porphyrin-based nanohoops, rings, and cages, which are difficult to synthesize but have desirable properties.
  • The authors describe a template-free method to synthesize a unique bithiophene-bridged porphyrin cyclophane, revealing its strained structure and electronic characteristics through X-ray analysis.
  • The resulting compounds exhibit interesting aromatic properties and reactivity, with the dication being globally aromatic and able to relieve strain through nucleophilic addition with chloride.
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Steric effects on the intramolecular charge transfer fluorescence of benzo[]thiophene-1,1-dioxide bridged macrocages.

Org Biomol Chem

July 2021

Division of Applied Chemistry, Faculty of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan.

Intramolecular charge transfer (ICT) fluorescence has been widely investigated and exploited in sensor molecules. However, steric effects on the ICT fluorescence properties have rarely been reported so far, although research in this area would promote an understanding of the basics of solvation. Herein, we report the detailed fluorescence properties of bis(trimethylsilyl)benzo[b]thiophene-1,1-dioxide (TMSBTO2) and its caged cyclophanes and non-cage isomers, which demonstrate ICT fluorescence in various solutions.

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We report the template-free synthesis and characterization of a new type of porphyrin/quinoidal-bithiophene-based conjugated macrocycle. X-ray crystallographic analysis of the dimer (2MC) revealed a cyclophane-like geometry with large dihedral angles between the porphyrin and the neighboring thiophene rings, and NMR measurements and theoretical calculations confirmed a localized aromatic character of the porphyrin/thiophene rings and quinoidal character of the bithiophene linkers. Restricted rotation of the thiophene rings linked to the porphyrin unit was observed by variable-temperature NMR measurements.

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We demonstrate a new synthetic strategy to cyclophanes containing thiophene and indole moieties via Grignard addition, Fischer indolization and ring-closing metathesis as key steps.

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From thiophene [2]rotaxane to polythiophene polyrotaxane.

J Am Chem Soc

July 2009

Functional Modules Group, Organic Nanomaterials Center, National Institute for Materials Science, Ibaraki, Japan.

The polythiophene polyrotaxane was synthesized through electrochemical polymerization of the [2]rotaxane consisting of the electron-rich dumbbell-shaped sexithiophene and the electron-deficient cyclophane of cyclobis(paraquat-p-phenylene). The optical and electrochemical property of the polythiophene polyrotaxane film was characterized. The material reported herein is attractive not only as a component for constructing the macromolecular machine but also as a new type of insulated molecular wire having donor-acceptor interaction between the macrocycle and the conductive polymer.

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