电子效应控制了非功能化基替代基的不对称化机制
Yubo Fan1, Xiuhua Cui, Kevin Burgess
1Department of Chemistry, Texas A & M University, Box 30012, College Station, TX 77842-3012, USA.
Journal of the American Chemical Society
|December 23, 2004
概括
密度函数理论计算揭示了复合物如何催化基的不对称化. 与连接体的亚达曼基群的固体相互作用主要决定了这些反应中的反面选择性.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 计算化学的计算化学
背景情况:
- 不对称的化对于合成性分子至关重要.
- 复合物与N-异环碳联体是有效的催化剂.
- 了解反应机制和选择性决定因素是催化剂设计的关键.
研究的目的:
- 阐明了基因的不对称化机制,这些基因被化物伊里伊米达索利丁氧化复合物催化.
- 为了研究在这种催化系统中控制反表面选择性的因素.
- 通过实验观察来验证计算预测.
主要方法:
- 使用PBE和B3LYP函数的密度函数理论 (DFT) 计算.
- 对基协调,迁移插入和产品释放步骤的建模.
- 对影响立体选择性的硬体和电子因素的分析.
主要成果:
- 基协调优先发生在转向碳联体的碳联体上.
- 化过程通过与H2和化物转移的连续反应进行.
- 与连接体的阿达曼基群的固体相互作用是三位置换基的反面面选择性的主要驱动因素.
结论:
- DFT模型准确地预测了实验观察到的enantioselectivities.
- 这项研究提供了对催化不对称化的机制理解.
- 干体的设计,特别是固态质量,对于控制反选择性至关重要.
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