胺催化阿尔多尔反应的过渡状态
Adam Simon1, Yu-Hong Lam1, K N Houk1
1Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
Journal of the American Chemical Society
|January 5, 2016
概括
密度函数计算显示,附近的胺催化阿尔多尔反应有利于循环过渡状态. 这种九个环的结构,特别是冠状结构,解释了这些化学反应中观察到的立体选择性.
科学领域:
- 有机化学
- 计算化学
背景情况:
- 阿尔多尔反应是有机合成中基本的碳-碳键形成反应.
- 邻胺是促进阿尔多尔反应的有效催化剂.
- 了解过渡状态对于控制反应结果和立体选择性至关重要.
研究的目的:
- 描述由近邻二胺催化的阿尔多尔反应的过渡状态.
- 阐明这些催化反应的立体选择性结构特征.
主要方法:
- 用密度函数理论 (DFT) 的计算来建模和分析反应途径.
- 过渡状态结构的优化和特征.
- 对过渡状态进行了合规分析.
主要成果:
- 一个周期性过渡状态涉及九个成员的结环被确定为首选的途径.
- 这种周期性过渡状态的皇冠 (椅子-椅子) 构造被发现是能量有利的.
- 这些特定的形状与实验观察到的立体选择性相关.
结论:
- 胺催化醇反应的首选过渡状态是九个成员的循环结构.
- 这些反应的立体化学结果是由过渡状态的冠状结构决定的.
- 计算方法为有机催化反应的机制提供了宝贵的见解.
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