超价基键催化在烯与醇的水利化上进行的超价基键催化计算研究:O-激活与π-激活
Chang Zhao1, Ying Li1, Wen-Kai Chen1
1College of Chemistry and Materials Science, Hebei Key Laboratory of Inorganic Nano-Materials, Hebei Normal University, Shijiazhuang 050024, China.
The Journal of organic chemistry
|February 14, 2025
概括
使用循环高价的基键催化,有利于O-激活水利化. 这种由静电相互作用驱动的机制解释了有机催化在有机催化过程中的偏好性产物形成.
科学领域:
- 机体催化剂是有机催化剂.
- 催化剂是一种催化剂.
- 计算化学计算化学
背景情况:
- 素键催化是有机催化的一个新兴领域,因其环保性和成本效益而受到重视.
- 超价化合物已显示出催化反应的潜力,例如 styrene 和 phenol 的化.
- 此前已经提出过超价基····催化.
研究的目的:
- 通过使用计算方法研究循环高价基催化剂催化和的化.
- 阐明反应机制,包括确定关键激活模式和能量障碍.
- 了解影响区域选择性的因素,特别是对 орто-hydroarylation 的偏好.
主要方法:
- 用密度函数理论 (DFT) 的计算来研究催化系统.
- 分析了两种不同的激活模式:对烯的π激活和对的O激活.
- 对不同反应路径和替代物效应的能量障碍进行了计算评估.
主要成果:
- 确定了两种激活模式,π激活和O激活.
- 与π激活模式相比,O激活模式的能量障碍较低,这表明它更有利.
- 对于O-激活模式,正态-水利化通路显示较低的能量障碍比对水利化,与实验观测一致,并归因于更强的静电相互作用.
结论:
- 建议O-激活模式作为由循环高价基催化剂催化的水利化更有利的途径.
- 较强的静电相互作用被确定为驱动观察到的正确选择性的关键因素.
- 这项研究提供了对这些催化剂的反应性和替代效应的见解,可能扩大了素键催化剂的应用.
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