在二甲基硫氧化物中重新检查了氨酸形成路径:通过NMR确定速率常量
Michael H Haindl1, Johnny Hioe1, Ruth M Gschwind1
1Institut für Organische Chemie, Universität Regensburg , D-93053 Regensburg, Germany.
Journal of the American Chemical Society
|September 22, 2015
概括
这项研究量化了酶胺形成率,揭示了DMSO的主要途径是iminium deprotonation. 酵素形成的动力学取决于实验条件,而不是核友的强度.
科学领域:
- 有机催化剂
- 化学动力学
- 反应机制
背景情况:
- 胺催化是一种关键的器官催化激活模式.
- 胺中间体至关重要,但它们的形成途径仍有争议.
- 拟议的机制包括iminium和/或oxazolidinone中间体.
研究的目的:
- 通过实验确定胺形成的速率常数和速率.
- 调查影响胺形成率的因素,包括氨酸,水和添加剂.
- 阐明胺形成的主要途径.
主要方法:
- 使用1D选择性交换光谱 (EXSY) 积累曲线.
- 在动力分析中使用初始速率近似值.
- 结合了实验动力数据和理论计算.
主要成果:
- 提出了第一个经过实验确定的胺形成速率常数.
- 确定了iminium中间体的脱质化为DMSO的主要途径.
- 证明胺的形成是proline和oxazolidinones的零级.
- 显示的添加剂核友性影响了佐利丁异构,而不是胺形成率.
结论:
- 主要的胺形成途径是条件依赖的,有利于DMSO中的胺脱质.
- 通过E2机制排除了氧化的直接脱质.
- 核素辅助的排泄不是主要的途径.
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