机理性理解铜催化化C-H键结中的意想不到的元选择性
Bo Chen1, Xue-Long Hou, Yu-Xue Li
1Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry , Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai 200032, China.
Journal of the American Chemical Society
|April 28, 2011
概括
铜催化化意外地通过Heck-like路径形成元产物. 一个 methoxy 组通过电友置换指导正体产物形成,得到了 Cu (I) 催化剂的动力学研究的支持.
科学领域:
- 有机金属化学 有机金属化学
- 反应机制 反应机制
- 计算化学的计算化学
背景情况:
- 铜催化C-N键的形成在有机合成中至关重要.
- 了解 arylation 反应中的区域选择性仍然是一个挑战.
研究的目的:
- 阐明化的铜催化化机制.
- 解释意想不到的元产品的形成.
- 调查替代效应对区域选择性的作用.
主要方法:
- 密度函数理论 (DFT) 的计算.
- 动力学研究.
- 实验反应监测.
主要成果:
- DFT 暗示了一个 Heck-like 四个成员环过渡状态,涉及 Cu(III) -Ph 种类的元产品形成.
- 一个具有竞争力的电友性替代机制在存在甲甲-甲氧基时产生正正产物.
- 实验证据,包括动力学数据,支持Cu (I) 催化剂的参与.
结论:
- 这项研究揭示了铜催化化物合的双重机制.
- 区域选择性是由替代物的电子效应和过渡状态几何学控制的.
- 建议使用Cu (I) /Cu (III) 催化循环.
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