通过Piano-Stool Ruthenium Carbene复合物形成的Enynes的化转化
Sebastian Peil1, Giovanni Bistoni1, Richard Goddard1
1Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
Journal of the American Chemical Society
|October 19, 2020
概括
内部基的双化是一种新的转化,其中两个原子添加到基的一种碳. 这种催化反应提供了循环化,转化和C-H功能化的途径.
科学领域:
- 有机金属化学
- 催化剂
- 合成有机化学
背景情况:
- 内的双化是一种最近发现的转化.
- 这种反应涉及从二转移到的单一碳原子.
- 该过程产生金属碳复合物作为反应性中间体.
研究的目的:
- 研究内部基的化机制和范围.
- 了解控制循环和转移途径之间的选择性因素.
- 将这种转化应用于天然产品的总合成,并探索新的合成应用.
主要方法:
- 使用[Cp*RuCl]4作为双质化的催化剂.
- 对各种进行了系统的调查,以确定反应结果.
- 在局部合集群理论层面进行计算研究以阐明反应机制.
- 通过X射线衍射分离和鉴定了一种鲁碳中间体.
主要成果:
- 氨酸的替代模式决定了是否发生循环化或转化.
- 开发了一种预测模型,将反应选择性与双键极化和碳复合物的稳定性联系起来.
- 在E和F共合成中首次应用"化转化"证实了拟议的结构.
- 双化还可以使C-H功能化和化基因参与化转化,从而产生基.
结论:
- 双胞胎化是一种基于电子和硬质因素的可预测选择性的多功能转化.
- 开发的模型为设计新的催化反应提供了宝贵的见解.
- 这种方法扩大了天然产品合成和制造有价值的有机化合物的合成可能性.
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