Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 75, Issue 24, Pages 8363-8371Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo101299x
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Funding
- National Science Foundation [CHE-0455575, CHE-9610347]
- Swiss National Science Foundation [2000-121747]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0741837, 840336] Funding Source: National Science Foundation
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Several routes for the synthesis of m-terphenyl thio-, seleno-, and telluroethers were investigated. m-Terphenyl iodides react with diphenyl diselenides or ditellurides (CsOH center dot H2O, DMSO, 110 degrees 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.
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