溶剂分子如何影响竞争的消除和替代动态. 对机理的洞察力 进化与增加的解法
Xu Liu1, Jiaxu Zhang1, Li Yang1
1State Key Laboratory of Advanced Welding and Joining, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering , Harbin Institute of Technology , Harbin 150001 , P. R. China.
Journal of the American Chemical Society
|July 4, 2018
概括
溶剂分子显著影响有机反应. 添加甲醇通过稳定过渡状态,将反应性从气相转移到溶液相动态,从而促进替代 (SN2) 而不是消除 (E2).
科学领域:
- 物理有机化学
- 计算化学
- 化学动力学
背景情况:
- 在有机合成中,竞争性SN2替代和E2消除反应至关重要.
- 单个溶剂分子在SN2/E2原子动态和反应性中的确切作用尚未完全理解.
研究的目的:
- 研究溶剂分子如何影响竞争SN2和E2反应的原子动态.
- 阐明溶解对反应机制和选择性的影响.
主要方法:
- 用于原型微溶系统的反应动态模拟:离子与乙烯化物反应.
- 与不同程度的甲醇溶解的无溶剂条件进行比较.
主要成果:
- 在无溶剂条件下,由于动态效应,E2消除机制意外地占据了SN2替代的优势.
- 一个单一的甲醇分子通过差异化溶液-溶剂相互作用稳定其过渡状态,从而显著增强SN2通路.
- 增加的溶解进一步促进SN2,同时显著抑制E2路径.
结论:
- 突出了反应能量学和动态学在确定机械选择性的关键相互作用.
- 由于溶解效应,反应从气相转移到溶液相环境,表明从消除到替代的一般过渡.
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