Synthesis and structure of m-terphenyl thio-, seleno-, and telluroethers

Uzma I. Zakai, Anna Błoch-Mechkour, Neil E. Jacobsen, Leif Abrell, Guangxin Lin, Gary S. Nichol, Thomas Bally, Richard S. Glass

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Abstract

Several routes for the synthesis of m-terphenyl thio-, seleno-, and telluroethers were investigated. m-Terphenyl iodides react with diphenyl diselenides or ditellurides (CsOH·H2O, DMSO, 110 °C) to give the desired compounds in 19-84% yield which significantly extends the previously reported such reactions because o-benzyne cannot be an intermediate as previously suggested. However, the most general synthetic route was that involving reaction of 2,6-diaryl Grignard reagents with sulfur, selenium, or tellurium electrophiles. The m-terphenyl thio-, seleno-, and telluroethers were characterized spectroscopically and, in one case, by single-crystal X-ray analysis. Certain of these compounds showed atropisomerism and barriers for interconversion of isomers were determined by variable-temperature NMR spectroscopy. The barriers for interconverting the syn and anti atropisomers increase on going from the analogous S to Se to Te compounds. Calculations on this isomerization revealed that the barriers are due to rotation about the aryl-aryl bond and that the barriers for rotation about the aryl-chalcogen bond are much lower.

Original languageEnglish (US)
Pages (from-to)8363-8371
Number of pages9
JournalJournal of Organic Chemistry
Volume75
Issue number24
DOIs
StatePublished - Dec 17 2010

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ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Zakai, U. I., Błoch-Mechkour, A., Jacobsen, N. E., Abrell, L., Lin, G., Nichol, G. S., Bally, T., & Glass, R. S. (2010). Synthesis and structure of m-terphenyl thio-, seleno-, and telluroethers. Journal of Organic Chemistry, 75(24), 8363-8371. https://doi.org/10.1021/jo101299x