从内部酸盐到终端酸盐的鲁催化迁移性半化
Lijuan Song1,2, Qiang Feng3, Yong Wang3
1Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics , Peking University Shenzhen Graduate School , Shenzhen 518055 , China.
Journal of the American Chemical Society
|October 10, 2019
概括
这项研究引入了一种新的基半化,产生有价值的终端基. 该过程为基提供了一种新的反应模式,并允许选择性结合或转化添加.
科学领域:
- 有机化学
- 催化剂
- 有机金属化学
背景情况:
- 半化为是一种关键的合成转化.
- 现有的方法主要产生 cis 或 trans 基.
- 需要新的方法来获取多种基结构.
研究的目的:
- 开发一种新的双质半化内部.
- 探索一种新型的基反应模式.
- 提供接入终端维尼尔丝兰.
主要方法:
- 使用了阴阳性[CpRu(MeCN) 3PF6催化剂.
- 使用各种基和基替代基.
- 最佳的反应条件包括基,添加剂和H2压力.
- 进行密度功能理论 (DFT) 研究以阐明机制.
主要成果:
- 实现了高效和宝石选择性半化.
- 通过条件优化将选择性从 geminal 转换为 trans 的能力.
- DFT计算表明一个gem-H2 Ru-carbene中间体是关键,而不是一个Ru-vinylidene.
- 控制实验支持了提出的机制.
结论:
- 通过双半和1,2-迁移建立了一个新的合成路径.
- 这项研究揭示了在催化下基的新型反应模式.
- 这些发现扩大了合成变化的工具箱.
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