铜 (II) 化物在 sp3 C-H 氨基化中
Eun Sil Jang1, Claire L McMullin, Martina Käß
1Department of Chemistry, Georgetown University , Box 571227-1227, Washington, D.C. 20057, United States.
Journal of the American Chemical Society
|June 19, 2014
概括
新型铜 (II) 化物促进了C-H氨基化反应. 这些复合物,当与过氧化物相结合时,使Kharasch-Sosnovsky反应的新变体能够用于功能化的氨酸合成.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 铜复合物是有机转化中的多功能催化剂.
- β-diketiminato联体为金属复合体提供可调节的硬质和电子特性.
- C-H氨化是引入功能到有机分子的关键反应.
研究的目的:
- 为了合成和描述新的β-diketiminato铜(II) 化物.
- 为了研究这些铜复合物的C-H氨化活性.
- 探索一种新的催化系统,用于合成功能化的anilines.
主要方法:
- 从铜中合成铜 (II) 化物 (II) 氧化物和各种化物.
- 使用X射线衍射进行结构性表征.
- 磁性易感性和电子磁共振 (EPR) 光谱学.
- 与碳化合物在 tert-butyl 氧化物存在或不存在的情况下发生的 C-H 氨基化反应.
主要成果:
- 合成和描述了具有多种结合模式 (κ(1) -N,桥接, κ(2) -N,N) 的新型铜(II) 化物.
- 仅仅使用铜化物时,静态测量C-H氨基化是无效的.
- 使用 tert-butyl过氧化物实现了快速的 C-H 氨基化,这表明涉及 tert-butoxide 基的基因途径.
- 铜化物作为基质清除剂,通过修改的Kharasch-Sosnovsky反应导致功能化的化物.
结论:
- 合成的β-diketiminato铜(II) 化物表现出各种协调行为.
- 这些复合物与过氧化物结合,使Kharasch-Sosnovsky反应的有效氨基变体成为可能.
- 这项研究提出了一种新的方法,通过铜催化C-H氨基化合成功能化的anilin.
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