Base‐Induced 1,3‐Sigmatropic Rearrangement of Mesitylphosphonium Salts
| العنوان: | Base‐Induced 1,3‐Sigmatropic Rearrangement of Mesitylphosphonium Salts |
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| المؤلفون: | Dominic S. Wright, Lucy K. Allen, Sophia A. Solomon, Sarah B. J. Dane |
| المصدر: | European Journal of Inorganic Chemistry |
| بيانات النشر: | Wiley, 2013. |
| سنة النشر: | 2013 |
| مصطلحات موضوعية: | chemistry.chemical_classification, Reaction mechanism, Base (chemistry), 010405 organic chemistry, Chemistry, Stereochemistry, Sigmatropic reaction, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Gas phase, Inorganic Chemistry, chemistry.chemical_compound, Deprotonation, Ylide, Phosphonium, Stoichiometry |
| الوصف: | Attempted synthesis of the ylide dianion [2,4,6-Me3C6H2P(CHR)3]2– (2,4,6-Me3C6H2 = mesityl, R = H or Me) by the reaction of mesitylphosphonium iodides [2,4,6-Me3C6H2PR3]+I– (R = Me, 1; R = Et, 2) with tBuLi at reflux does not result in the anticipated deprotonation of the phosphorus-bonded R groups. Instead, quantitative 1,3-sigmatropic rearrangement occurs to give new benzylic phosphonium salts [(3,5-Me2C6H3)CH2PR3]+I– (R = Me, 6; R = Et, 7), in which the phosphonium centre, the R3P group, is transferred to an ortho-CH3 group. In situ 31P NMR spectroscopic studies show that the reaction is base-activated and stoichiometric with respect to tBuLi. DFT calculations support the conclusion that the rearrangement is thermodynamically favourable in the gas phase and in THF and show that the rearrangement is enthalpically driven. |
| تدمد: | 1099-0682 1434-1948 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::61642677a07f966ab51a4cf7e2ae0623 https://doi.org/10.1002/ejic.201301203 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....61642677a07f966ab51a4cf7e2ae0623 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 10990682 14341948 |
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