对替代的CC双键进行甲基基的添加反应
Yuman Hordijk1, Tula M M Kaptein1, Eva Blokker1
1Department of Chemistry and Pharmaceutical Sciences, Amsterdam Institute for Molecular and Life Sciences (AIMMS), Vrije Universiteit Amsterdam, De Boelelaan 1108, Amsterdam 1081 HZ, The Netherlands.
对替代乙烯的甲基基添加反应 (MRAR) 由于减少排斥和增强轨道相互作用,有利于在β-碳的添加. 像CHO和NMe2这样的替代物通过改变电子效应和改善轨道相互作用来调节反应性.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
- 反应机制 反应机制
背景情况:
- 极端加法反应对于碳-碳键的形成至关重要.
- 了解这些反应的规则对于合成化学至关重要.
研究的目的:
- 研究对单替代乙烯的基本甲基基添加反应 (MRAR).
- 分析影响区域选择性和替代效应的因素.
- 提升对激素加法反应的机理性理解.
主要方法:
- 密度函数理论 (DFT) 的计算使用ZORA-(U) OLYP/TZ2P.
- 激活应变模型 (ASM) 和能量分解分析 (EDA).
主要成果:
- 根基加法优先发生在β-碳而不是α-碳.
- 减少了保利排斥和最大化轨道相互作用有利于β-加法.
- 电子捐赠 (NMe2) 和电子吸收 (CHO) 组通过改善的轨道相互作用来降低激活障碍.
- 由于轨道相互作用机制的改变,CHO显示了比NMe2更大的屏障降低.
结论:
- 提供了对MRAR.中的区域选择性和替代效应的机制性理解.
- 将定性理论 (例如,前沿分子轨道理论) 与计算洞察力联系起来.
- 为理解激进加法转换提供了一个物理上健全的基础.
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