单基-基[n]urils (n = 5,6,7,8) 的综合合成:高纯度和高转化率
Mehmet M Ayhan1,2, Hakim Karoui1, Micaël Hardy1
1†Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, 13397 Marseille, France.
Journal of the American Chemical Society
|July 22, 2015
概括
一种新的光化学方法可以使用过氧化和紫外线来实现高产单醇功能化. 这种可扩展的技术为反应机制提供了洞察力,并产生了新的CB[n]衍生物.
科学领域:
- 有机化学
- 摄影化学
- 超分子化学
背景情况:
- 黄瓜 (CB[n]) 是具有有限合成修饰选项的宏循环宿主.
- 开发有效的CB[n]功能化方法对于扩大其应用至关重要.
研究的目的:
- 开发一种新的光化学方法来直接单功能化.
- 调查功能化过程的反应机制和扩展潜力.
主要方法:
- 使用过氧化和紫外线进行光化学反应.
- 旋转捕捉和质谱 (MS) 用于基质的表征.
- 同位素标记的水实验 ((18) O).
- 密度函数理论 (DFT) 对债券分离能量的计算.
主要成果:
- 在CB[5],CB[6],CB[7]和CB[8]的直接酒精功能化中实现了95%-100%的转化.
- 成功将反应扩大到CB[6]和CB[7].
- 在反应机制中确定了基和离子中间体.
- DFT的计算解释了赤道C-H债券的优先反应和与CB的挑战[8].
- 获得CB[5]-(OH) 1和第一个CB[8]衍生物,CB[8]-(OH) 1,产量很好.
结论:
- 开发的光化学方法提供了一种简单而高效的合成单功能性库库比的途径.
- 这项研究为CB[n]功能化所涉及的基和离子通路提供了机械的洞察力.
- 这项工作扩大了功能化,特别是CB的合成可访问性[8].
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