催化有氧氧化N-N合碳素和二胺,包括选择性交叉合
Michael C Ryan1, Joseph R Martinelli2, Shannon S Stahl1
1Department of Chemistry , University of Wisconsin-Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States.
Journal of the American Chemical Society
|July 11, 2018
概括
一种新的铜催化方法使得碳素和二胺的有氧氧化二聚化成为N-N合产品. 这种反应具有显著的选择性,通过可逆中间体有利于热力学稳定的交叉合产品.
科学领域:
- 有机化学
- 催化剂
- 合成方法
背景情况:
- 碳醇和二胺是重要的含异环.
- 氧化二元化反应对于形成C-N和N-N键至关重要.
- 开发这些转换的选择性催化方法仍然是一个挑战.
研究的目的:
- 开发一种新的铜催化方法,用于碳素和二胺的有氧氧化二聚化.
- 研究这些基质之间的交叉合反应的选择性.
- 阐明观察到的选择性背后的机制.
主要方法:
- 使用铜二甲硫化催化剂与N,N-二甲胺.
- 使用的有氧条件为1 atm,温度为60-80°C.
- 使用标准有机合成技术和光谱方法分析反应产物.
主要成果:
- 实现了碳醇和二氨酸的有效N-N合,形成双碳醇和四氨酸.
- 在carbazole和diarylamines之间的交叉合反应中表现出异常高的选择性,比例为1:1.
- 确定可逆的四基形成是选择性的关键,有利于热力学稳定的产品.
结论:
- 已经建立了一种温和而高效的Cu催化有氧氧化二元化方法.
- 该反应对交叉合产品具有很好的选择性,由可逆中间机制驱动.
- 这项工作为N-N合异环提供了有价值的合成途径,在材料科学和药物化学中具有潜在的应用.
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