局部抗芳热点驱动双基和单基的减少性脱循环
Zheng Zhou1,2, Dominic T Egger3, Chaowei Hu4
1Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, United States.
Journal of the American Chemical Society
|June 2, 2022
概括
我们开发了一种新的还原循环化方法, 这种简单的环闭是由反芳香的缓解驱动的,扩大了合成的可能性.
科学领域:
- 有机化学
- 材料科学
- 超分子化学
背景情况:
- 是具有独特螺旋结构的多环芳.
- 阳离子石墨烯子单位是先进碳材料的重要组成部分.
- 抗芳香性对循环系统的反应性和稳定性起着重要作用.
研究的目的:
- 开发一种用于合成复杂的离子石墨烯子单元的新型降解脱循环法.
- 研究这些循环反应背后的机制和驱动力.
- 探索反芳香性对过程的区域选择性和效率的影响.
主要方法:
- 具有嵌入五个环的单和双的减少脱循环.
- 用分子氧中断反应级联.
- 计算分析包括MO分析,分子静电电位图和NICS ((1.7) ZZ计算.
主要成果:
- 形成七环,非环和十环离子石墨烯子单元.
- 对于双基的完全双重取消或中断循环路径的证明.
- 证实抗芳香性减轻是易于封闭环的主要驱动力.
- 在指导电荷和创建反芳香热点方面确定环二烯基部分的作用.
- 通过对较少张力单烯的研究验证抗芳香性缓解的作用.
结论:
- 减少脱循环提供了复杂的离子石墨烯子单元的多功能途径.
- 反芳香性是控制这些反应的区域选择性和效率的关键因素.
- 这种方法为构建多环芳香系统提供了传统的舒尔反应的有价值的替代方案.
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