氧化的分子内1,3-二极反应通过循序渐进的1,1-循环添加/逆机制发生
1Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Journal of the American Chemical Society
|November 6, 2003
概括
密度函数理论揭示了氧化物和基之间的分子内1,3双极反应是一个三步过程. 竞争反应可能占主导地位,特别是在较长的绳索或缺少替代品的情况下.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
背景情况:
- 分子内1,3-双极反应是关键的合成转化.
- 氧化物是用于循环添加反应的多功能1,3-二极体.
研究的目的:
- 使用计算方法阐明氧化和之间的分子内类似反应的反应机制.
- 确定影响分子内反应与其他反应途径之间的竞争因素.
主要方法:
- 用密度函数理论 (DFT) 的计算来研究反应路径.
- 对反应中间体和过渡状态进行了分析.
主要成果:
- 反应通过三步机制进行,包括加碳化物和反反应.
- 确定了一种双循环酸盐化合物和一种酸盐cyclopropane中间体的形成.
- 发现分子内 (3+2) 循环添加和分子间氧化二元化对furoxans是竞争性的途径.
- 反应结果对带的长度和像三甲基酸这样的替代物的存在都很敏感.
结论:
- 这项研究提供了对分子内1,3-双极反应的详细机制理解.
- 反应条件,包括基质结构,显著影响对所需反应的选择性.
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