对于过渡金属促进的烯-烯循环添加,是否需要芳香性损失?
João V Schober1, Croix J Laconsay1, Judy I Wu1
1Department of Chemistry, University of Houston Houston TX 77204 USA jiwu@central.uh.edu jvoliveisoares@uh.edu.
Dearomatization是竞技场像竞技场一样反应的关键. 计算研究表明,只有当体失去芳香性 (去芳香化) 时,它们才能经历具有低能量障碍的循环添加反应.
科学领域:
- 有机化学 有机化学
- 计算化学计算化学
- 反应机制 反应机制
背景情况:
- 烯通常具有芳香性,限制了它们在循环添加反应中的参与.
- 了解的反应性对于设计新的合成途径至关重要.
研究的目的:
- 为了调查 dearomatization 在使arene 循环添加反应成为可能的作用.
- 计算反应概况和分析替代和金属复合体领域的结合.
主要方法:
- 计算的气相反应概况.
- 核独立化学转移 (NICS) 的计算.
- 对于各种竞技场协调模式 (η2, η4, η6) 的结合分析.
主要成果:
- Dearomatization 是一个先决条件,以展现 ene 和 diene 类似的反应性.
- 替代和n6场对循环添加具有很高的能量障碍.
- 强烈脱芳的n2和n4场表现出低的自由能量障碍 (≤20 kcal mol-1) 对 [4+2] 循环添加.
结论:
- 竞技场需要 dearomatization 经历迪尔斯-阿尔德类型反应.
- dearomatization 的程度决定了循环添加的能量屏障.
- 这一发现为涉及的新型合成转化提供了可能性.
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