化物作为可调节的试剂,用于基胺和氨基碳化
Jean-Grégoire Roveda1, Christian Clavette, Ashley D Hunt
1Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K1N 6N5.
Journal of the American Chemical Society
|June 10, 2009
概括
基化物在高温下经历分子内胺化. 试剂结构的修改导致氨基碳化物产物,其中一个反应证明了立体特异性.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 基化物是热稳定的试剂.
- 它们在高温下的反应性对合成转化有兴趣.
研究的目的:
- 为了研究类化的高温反应.
- 探索试剂结构对反应结果的影响.
主要方法:
- 在120-235°C的温度下加热化化物.
- 使用密度函数理论 (DFT) 计算进行计算分析.
- 酸化试剂的结构修改.
主要成果:
- 在120-235°C时从基化物 (R = Ph) 中获得了分子内胺化产物.
- 建议采用协同的Cope型水氨基化,然后通过水化物中间体进行质子转移.
- 氨基化产品在200°C时更喜欢使用改性试剂 (R = Ot-Bu或NH ^ 2)).
- 发现与R = NH(2) 的氨基碳化反应是立体的.
结论:
- 酸化在高温下表现出独特的反应性.
- 试剂结构决定了反应路径,导致胺化或氨基化.
- 涉及Cope型重组和ylide中间体的拟议机制得到了DFT计算的支持.
相关概念视频
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