Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume 2012, Issue 16, Pages 3132-3141Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.201200176
Keywords
Chromium; Rearrangement; Anionic thia-Fries rearrangement; Arynes; Lithiation; Phenyl triflate; Haloarenes
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Funding
- Deutsche Forschungsgemeinschaft (DFG) [BU 814/16-1]
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The generation of (eta 6-aryne)chromium complexes as reactive intermediates was investigated in two ways. Although earlier attempts directed towards triflate eliminations from a variety of tricarbonyl(phenyl triflate)chromium complexes had failed, more electron-rich phenyl triflate complexes were considered. This was accomplished either by substitution with two methoxy groups in the arene ligand or by replacement of one of the three carbonyl ligands of the tricarbonylchromium complex with triphenylphosphane. However, the attempted elimination still did not take place; in spite of the increased electron densities in the aromatic ligands, anionic thia-Fries rearrangements were observed in high yields at 78 degrees C. As an alternative, elimination of lithium fluoride was tested. Tricarbonyl(2-lithiofluorobenzene)chromium(0) was generated by tin/lithium exchange. After hydrolytic workup, tricarbonyl(fluorobenzene)chromium was obtained as the main product, indicating that the lithiation step had been successful. A dimeric side product provided evidence for the intermediacy of (benzyne)tricarbonylchromium.
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