(II/IV) 多重使室温 C (sp3) -H 功能化
Courtney C Roberts1, Eugene Chong1, Jeff W Kampf1
1Department of Chemistry , University of Michigan , 930 North University Avenue , Ann Arbor , Michigan 48109 , United States.
Journal of the American Chemical Society
|November 27, 2019
概括
研究人员在室温下使用高价催化剂实现了轻度C(sp3) -H激活. 这一过程产生稳定的-IV中间体,使多种C-H功能化反应成为可能.
科学领域:
- 有机金属化学
- 催化剂
- 合成化学
背景情况:
- 在有机合成中,C(sp3)-H激活至关重要.
- 催化C-H激活通常需要恶劣的条件或特定的Ni氧化状态.
研究的目的:
- 通过使用高价中心来证明温和的室温C ((sp3) -H激活.
- 探索这种新变化的机制和范围.
- 开发一种催化C(sp3) -H功能化反应.
主要方法:
- 在高价复合物中氧化诱导C ((sp3) -H激活.
- 尼克尔-IV西格玛-复合物的分离和特征.
- 密度函数理论 (DFT) 的计算以阐明反应机制.
- 固态测量和催化C ((sp3) -H功能化反应.
主要成果:
- 在高价中心实现了温和的室温C ((sp3) -H激活.
- 一个可分离的-IV西格玛-复合物被生成.
- DFT研究发现了两种可能的机制,其中Ni-IV途径略受青.
- Ni-IV中间体与各种核友反应形成C(sp3) -X键.
- 证明了一种Ni (II/IV) 催化C (sp3) -H功能化.
结论:
- 在室温下对高价进行轻度C(sp3) -H激活是可行的.
- 产生的Ni-IV中间体是C-X键形成的多功能物种.
- 这项工作为开发新的催化C-H功能化策略提供了基础.
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