半三明治基复合物 链接转和内部基的宝石
Alexandre Guthertz1, Markus Leutzsch1, Lawrence M Wolf1
1Max-Planck-Institut für Kohlenforschung , Mülheim/Ruhr 45470, Germany.
Journal of the American Chemical Society
|February 13, 2018
概括
催化剂通过内部的转实现E-合成. 一项机械研究揭示了金属cyclopropene和carbene中间体,解释了竞争中的宝石化和产品形成途径.
科学领域:
- 有机金属化学
- 催化剂
- 反应机制
背景情况:
- 内的化通常产生Z-.
- 基于Cp*Ru的催化剂表现出异常的立体选择性,形成E-基.
- 这种非正统的转的确切机制尚不清楚.
研究的目的:
- 使用基于[Cp*Ru]的催化剂阐明内部基化的综合机械路径.
- 研究关键中间体的形成和命运,包括金属cyclopropenes和碳素.
- 了解转和宝石之间的竞争因素.
主要方法:
- 结合实验调查和计算研究 (密度函数理论 - DFT,合集群 - CCSD).
- 核磁共振 (NMR) 谱学对诱导的极化转移 (PHIP).
- 碳中间体的隔离和X射线衍射特征,特别是与propargylic-OR组.
主要成果:
- 主要形成一个金属cyclopropene中间体,通过协同转移H2导致E-.
- 一个竞争的途径通过基结的正式化形成基中间体.
- 碳中间体可以导致E-,定位异构体,,或经历进一步的反应,如环和环扩张.
结论:
- 该研究提供了[Cp*Ru]催化的详细机制理解,将实验观测与理论预测结合起来.
- 通过宝石化形成碳中间体解释了竞争的途径,并使新的合成转化成为可能.
- 实现了高选择性转醇,证明了制剂的实用性.
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