石化替代剂对经过伯格曼循环的内地因子的影响
Marcos Hendler1, Travis Greene1, Dominic A Sirianni2
1Department of Chemistry, Gottwald Center for the Sciences, University of Richmond, Richmond, Virginia 23173, United States.
石化替代剂降低了enediynes中的伯格曼循环的能量. 氧,硫和的同源体显示出有利的循环能量,特别是硫和.
科学领域:
- 计算化学计算化学
- 有机化学 有机化学
- 量子化学 是一个量子化学.
背景情况:
- 恩埃迪因是具有独特反应性的多功能有机分子.
- 伯格曼循环化是enediyne化学中的一个关键反应.
- 石化替代剂可以改变分子性质和反应性.
研究的目的:
- 从理论上研究含有石化的基因的电循环路径.
- 分析两个不同的循环化机制的几何和能量.
- 为了评估氧气,硫和替代剂对反应能量的影响.
主要方法:
- 使用BS-(U)CCSD/cc-pVDZ理论水平进行量子化学计算.
- 旋转-翻转 (SF) 运动方程合集群 (EOM-CC) 对二极能量的计算.
- 对反应途径的分析,包括伯格曼循环和石化-循环.
主要成果:
- 相比于母体enediyne,基替代剂显著降低了伯格曼循环化能量.
- 氧,硫和的同源体呈现下降的伯格曼循环化能量 (+6.07, +3.71, +3.47 kcal/mol,分别).
- 双循环产品对硫 (-5.50 kcal/mol) 和 (-9.05 kcal/mol) 的同源具有有利的能量.
结论:
- 结合了基基组,便于在enediynes中进行电循环反应.
- 硫和替代剂在稳定循环产品方面特别有效.
- 该研究证实了研究结构的芳香性和地面状态波函数性质.
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