了解和量化溶解物-溶剂范德瓦尔斯相互作用对非对称催化转换选择性的影响
Riya Kayal1, Lorenzo Baldinelli2, Ingolf Harden1
1Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm Platz 1 45470 Mülheim an der Ruhr Germany ingolf.harden@mpg.kofo.de.
Chemical science
|January 13, 2025
概括
溶液溶剂的范德瓦尔斯力对有机催化剂中的酶选择性影响最小. 先进的计算工具揭示了特定的相互作用,建议在催化剂设计中调整溶剂.
科学领域:
- 有机化学 有机化学
- 计算化学计算化学
- 物理化学 物理化学
背景情况:
- 酵素选择性有机催化主要使用无极或弱极的有机溶剂.
- 德瓦尔斯力对反应动力学和选择性的影响尚不清楚.
研究的目的:
- 为了研究在有机催化中的过渡状态水平上溶解物-溶剂范德瓦尔斯相互作用的性质和强度.
- 开发用于分析化学反应中溶剂效应的计算工具.
- 为了探索这些相互作用对酶选择性的影响,使用一种性布伦斯特德酸催化反应作为案例研究.
主要方法:
- 使用先进的计算化学工具来分析过渡状态.
- 作为模型系统,选择了一种特定的非对称的有机催化转换,这种转换由一种性布伦斯特德酸催化.
- 分析的重点是分散力和过渡状态和溶剂分子之间的短距离排斥.
主要成果:
- 在过渡状态和溶剂之间观察到强烈的分散相互作用,本地化在特定的催化剂组上.
- 短距离的排斥往往抵消了分散力,导致对enantioselectivity的总体影响最小.
- 对于某些过渡状态几何形状,观察到对特定反应通道的显著影响.
结论:
- 溶解剂-溶解剂范德瓦尔斯力对有机催化剂中的反选择性具有有限但取决于配置的影响.
- 将溶剂的结构和电子特性集成到催化剂设计中可以提高选择性.
- 开发的计算工具为研究各种科学学科中溶剂效应提供了新的可能性.
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