在高度中形成二甲基乙烯
Franck Le Vaillant1, Edward J Reijerse2, Markus Leutzsch1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr 45470, Germany.
Journal of the American Chemical Society
|November 4, 2020
概括
这项研究表明, (I2) 在催化以太合成中不会直接形成C-sp3-OC-sp3键. 一个稳定的 (III) 中间体优先形成C (sp3) -I键,使循环形成.
科学领域:
- 有机金属化学
- 催化剂
- 有机合成
背景情况:
- 从6个成员的氧基环中研究了I2促进的循环乙烯形成.
- 之前的报道建议通过减少性消除直接形成C ((sp3) -OC ((sp3).
研究的目的:
- 阐明I2促进的循环乙烯形成的机制.
- 识别反应性中间体并了解在催化循环中的作用.
主要方法:
- 使用光谱 (NMR,EPR) 和晶体分析进行详细的机械研究.
- 一种偏磁双金属Ni (III) 中间体的分离和表征.
- 在不同温度下进行中间体的热分解研究.
主要成果:
- 一种稳定的,具有Ni2Or2核和μ-桥的磁性双金属Ni (III) 中间体被分离和特征化.
- 该中间体在 -10 °C以上分解,产生消除产物和醇,表明偏好的C ((sp3) -I键的减少性消除.
- 循环THF环形成是通过将酒精/氧化物循环转化为C ((sp3) -I键.
结论:
- 通过使用I2进行降解的直接C(sp3) -OC(sp3) 键形成可能不起作用.
- 使用F+氧化剂可以在高价中心挑战C(sp3) -OC(sp3) 键的形成,从而最大限度地减少副作用.
- 这项研究使得通过还原性消除合成乙成为可能,而这在催化之前是一项具有挑战性的成就.
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