皮里顿离子的两样反应性
1Department Chemie, Ludwig-Maximilians-Universität, Butenandtstrasse 5-13, 81377 München, Germany.
Journal of the American Chemical Society
|October 15, 2010
概括
这项研究研究了2和4二离子与电友的反应性,揭示了溶剂对核友性和区域选择性的影响. 银离子是一种银离子.
科学领域:
- 有机反应动力学 有机反应动力学
- 两性核反应能力的核反应
- 皮里顿阳离子的化学成分
背景情况:
- 两性核友的反应性,如胺离子,是复杂的,取决于各种因素,包括电友和反应条件.
- 了解支配区域选择性 (N-与O-攻击) 的因素对于合成化学至关重要.
- 之前的研究已经探索了具有不同电友的皮里顿离子的行为,但缺乏统一的机械学理解.
研究的目的:
- 为了研究2和4皮里离子与水离子和迈克尔受体的反应的动力学和区域选择性.
- 确定皮里顿离子的核友性参数,并将其与电友性质相关联.
- 阐明溶剂,对电离子和电友结构对反应结果的作用,并修改现有的机械模型.
主要方法:
- 在DMSO,乙和水中的动力学研究.
- 使用电友性参数 (E) 和核友性参数 (N,s) 的相关性分析.
- 量子化学计算 (MP2/6-311+G(2d,p)) 来评估N-与O-攻击的热力学和内在偏好.
- 马库斯理论的应用,以合理化区域选择性.
主要成果:
- 与有机溶剂相比,在水中,皮里顿离子的核性显著降低.
- 速率常数与电友性参数线性相关,使得可以确定胺离子核友性参数.
- 高度反应的电友会导致N和O攻击产品与2-皮里离子的混合,以及与4-皮里离子的O攻击.
- 2-皮里顿离子是一个更强的核友,但一个较弱的易斯基比4-皮里顿离子.
- 量子计算表明N-攻击的热力学优势,但O-攻击的内在优势.
- 银离子对区域选择性的作用归因于原子阻断,而不是电友电荷增强.
结论:
- 溶剂的极性显著影响着二阳离子的核友性.
- 基于马库斯理论的统一理论框架成功地合理化了观察到的区域选择性.
- 已经澄清了银离子介导的区域选择性逆转的机制,修订了硬和软酸/框架内的解释.
相关概念视频
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