在密苏诺布反应的密度功能研究
Stephan Schenk1, Jennie Weston, Ernst Anders
1Institut für Organische Chemie und Makromolekulare Chemie der Friedrich-Schiller-Universität, Humboldtstrasse 10, D-07743 Jena, Germany.
Journal of the American Chemical Society
|September 8, 2005
概括
这项研究揭示了Mitsunobu反应.
科学领域:
- 有机化学 有机化学
- 计算化学计算化学
背景情况:
- 三obu反应是一种广泛使用的有机反应,用于形成.
- 它的立体化学结果一直是持续研究和辩论的主题.
研究的目的:
- 用计算方法广泛研究三obu反应的反应超表面.
- 阐明三obu反应的详细机制和立体化学路径.
主要方法:
- 密度函数理论 (DFT) 在BP86/6-311++G(3df,3pd) 层面的计算.
- 对反应中间体,过渡状态和潜在能量表面的分析.
主要成果:
- 确定了初始步骤的两个稳定的途径,形成一个氧化酸或贝他因.
- 揭示了两个关键的中间体,即平衡中的dialkoxyphosphorane和acyloxyalkoxyphosphorane.
- 证明反应可以通过SN2 (逆转) 或保留机制进行,这取决于中间体和条件.
- 显示了反应超表面的复杂性和选择性立体控制的潜力.
结论:
- 三obu反应机制比以前理解的要复杂得多.
- 反应基本上能够进行立体化学的反转或保留.
- 在Mitsunobu反应中,有机会实现选择性的立体化学控制.
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