对于 (2-乙氨基) 三烯循环的两个不寻常的竞争机制:伪甲酸相对于环周反应活性
David B Kimball1, Rainer Herges, Michael M Haley
1Department of Chemistry, University of Oregon, Eugene, Oregon 97403-1253, USA.
Journal of the American Chemical Society
|February 21, 2002
概括
高温循环化 (2-乙烯基) 二烯产生醇,而较低温度的铜催化只形成异因达,揭示了不同的反应途径.
科学领域:
- 有机化学 有机化学
- 异环化学 异环化学
背景情况:
- 三烯是有机合成中的多功能前体.
- 控制功能化三的循环化途径对于访问多样化的异环基架至关重要.
研究的目的:
- 在不同的条件下研究 (2-乙烯基) 三的反应途径.
- 阐明导致诺林和异因达醇形成的机制.
主要方法:
- 在ODCB.中进行热循环.
- 铜 ((I) 在1,2-二chloroethane中的化物催化循环.
- 密度函数理论 (DFT) 的计算.
- 标签研究. 标签研究.
主要成果:
- 通过在200°C的热循环形成单独的奇诺林.
- 通过在50°C的CuCl催化,单独形成异能工.
- 在热循环中识别一个3-dehydrocinnolinium离子中间体.
- 强有力的证据表明,在isoindazole形成过程中存在一个carbene中间体.
结论:
- 反应条件决定了 (2-乙烯基) 三的循环化结果.
- 不同的机制,涉及周环和伪甲状腺过渡状态,分别导致肉素和异构醇.
相关概念视频
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