1,3-二极性化物对应力基和基的循环添加中的反应性和区域选择性:一项计算研究
Franziska Schoenebeck1, Daniel H Ess, Gavin O Jones
1Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
本研究使用计算方法探索1,3-双极循环加法. 环基因比环基因更具反应性,反应性受环形大小和替代剂的影响.
科学领域:
- 计算化学计算化学
- 有机反应机制 有机反应机制
- 物理有机化学 有机化学
背景情况:
- 1,3-双极循环添加是有机合成中的关键反应.
- 了解过渡状态和激活障碍可以为反应设计提供信息.
- 循环基因和循环基因作为重要的双极化物.
研究的目的:
- 以计算方式研究涉及亚酸的1,3-双极循环添加的过渡状态和激活障碍.
- 分析替代剂和环大小对环基因和环基因反应性的影响.
- 为了比较不同亚酸的反应性,并探索这些循环添加反应中的区域选择性.
主要方法:
- 密度函数理论 (DFT) 使用B3LYP函数.
- 旋转元件缩放第二阶段莫勒-普莱塞特扰动理论 (SCS-MP2).
- 导体类极化连续模型 (CPCM) 用于溶解效应.
主要成果:
- 在循环环上用替代可显著增强反应性.
- 亚酸循环添加到循环催化素中显示了气相中的1,5-添加区域化学,在溶液中丢失.
- 随着环形大小的减少,循环基因的活性会增加,这是扭曲/相互作用模型解释的.
- 环基因是比环基因更有反应性的二极体.
- 皮克利亚化物表现出较低的激活障碍比亚化物.
- 反应性的差异主要是由于扭曲能量而不是应变释放.
- 转环烯比 cis 环烯更具反应性.
结论:
- 计算方法准确地建模了1,3-双极循环加法反应性.
- 环基因的反应性强烈依赖于环应变和替代效应.
- 了解过渡状态能量是预测和控制循环加法反应的关键.
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