Bifunctional Catalysis and Apparent Stereoelectronic Control in Hydrolysis of Cyclic Imidatonium Ions
| العنوان: | Bifunctional Catalysis and Apparent Stereoelectronic Control in Hydrolysis of Cyclic Imidatonium Ions |
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| المؤلفون: | Charles L. Perrin, and Richard E. Engler, David B. Young |
| المصدر: | Journal of the American Chemical Society. 122:4877-4881 |
| بيانات النشر: | American Chemical Society (ACS), 2000. |
| سنة النشر: | 2000 |
| مصطلحات موضوعية: | General Chemistry, Alkylation, Biochemistry, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Hydrolysis, Colloid and Surface Chemistry, chemistry, Amide, Carbonate, Bicarbonate Ion, Organic chemistry, Bifunctional, Selectivity |
| الوصف: | To test stereoelectronic control in cleavage of tetrahedral intermediates, cyclic imidatonium ions were hydrolyzed in buffered aqueous media. In carbonate buffer >97% amino ester was observed, as previously reported. However, in borate buffers 65−91% hydroxy amide was observed from five-membered-ring imidatonium ions, except for a highly alkylated one. Selectivity is attributed to leaving-group ability. Stereoelectronic control does operate in six-membered rings but provides only 2 kcal/mol toward rate acceleration. Production of amino ester in carbonate buffers is due to the bifunctional nature of bicarbonate ion and thus cannot be used to support a large stereoelectronic contribution. The geometrical requirements for bifunctional catalysis further imply the intermediacy of conformations counter to stereoelectronic control. |
| تدمد: | 1520-5126 0002-7863 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::9bc2327c0d92f11c2c821029c4da6bfe https://doi.org/10.1021/ja993771f |
| رقم الأكسشن: | edsair.doi...........9bc2327c0d92f11c2c821029c4da6bfe |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15205126 00027863 |
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