Fragmentation of the Conjugate Base of 2-(1-Hydroxybenzyl)thiamin: Does Benzoylformate Decarboxylase Prevent Orbital Overlap To Avoid It?
| العنوان: | Fragmentation of the Conjugate Base of 2-(1-Hydroxybenzyl)thiamin: Does Benzoylformate Decarboxylase Prevent Orbital Overlap To Avoid It? |
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| المؤلفون: | Ronald Kluger, Qingyan Hu |
| المصدر: | Journal of the American Chemical Society. 126:68-69 |
| بيانات النشر: | American Chemical Society (ACS), 2003. |
| سنة النشر: | 2003 |
| مصطلحات موضوعية: | Pyrimidine, Carboxy-Lyases, Chemistry, Decarboxylation, Stereochemistry, Protonation, General Chemistry, Biochemistry, Catalysis, Benzoylformate decarboxylase, Kinetics, chemistry.chemical_compound, Colloid and Surface Chemistry, Fragmentation (mass spectrometry), Mandelic Acids, Thiamine, Thiazole, Nuclear Magnetic Resonance, Biomolecular, Carbanion, Conjugate |
| الوصف: | The base-catalyzed addition of thiamin to benzaldehyde produces 2-(1-hydroxybenzyl)thiamin (HBnT), but in neutral solution HBnT undergoes base-catalyzed irreversible fragmentation into pyrimidine and thiazole derivatives. The fragmentation (rather than elimination) occurs in proportion to the extent that N1' is protonated or alkylated. Generating the conjugate base of HBnT by decarboxylation surprisingly leads to fragmentation independent of the state of N1'. Therefore, a cationic state at N1' specifically promotes removal of the C2alpha proton rather than the fragmentation process itself. It is suggested that benzoylformate decarboxylase, which generates a similar intermediate, exerts stereoelectronic control of the conformation of the carbanion, blocking fragmentation and facilitating protonation. |
| تدمد: | 1520-5126 0002-7863 |
| الوصول الحر: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::83bcb487dd115802fb12ff5de1bb760dTest https://doi.org/10.1021/ja0390505Test |
| رقم الانضمام: | edsair.doi.dedup.....83bcb487dd115802fb12ff5de1bb760d |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15205126 00027863 |
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