使用β-碳基替代基的Rh ((DPEPhos) 催化基化:机械洞察力导致低催化剂负载,使得在格拉姆级别上进行选择性催化
James Barwick-Silk1, Simon Hardy2, Michael C Willis1
1Department of Chemistry, Chemistry Research Laboratories , University of Oxford , Mansfield Road , Oxford OX1 4TA , U.K.
Journal of the American Chemical Society
|May 16, 2018
概括
本研究详细介绍了使用催化剂与1-octyne的β-amido-aldehyde的水酸化机制. 降低催化剂负载可以提高酸酶的选择性,而不是基环化.
科学领域:
- 有机金属化学
- 催化剂
- 反应机制
背景情况:
- 水酸化是形成碳-碳键的关键反应.
- 了解反应机制对于催化剂优化至关重要.
- 竞争的副作用,如循环三元化,可以降低产品的产量和选择性.
研究的目的:
- 阐明与1-octyne的β-amido-aldehyde的催化水酸化的详细机制.
- 调查酸和酸环化途径之间的相互作用.
- 在低催化剂负载下优化反应条件以获得高选择性和产量.
主要方法:
- 使用[Rh-cis-κ2-P,P-DPEPhos][乙]2][BArF4]基催化剂进行详细的机制研究.
- 动态研究包括初始速率测量和动态同位素效应 (KIE).
- 标记实验以追踪反应途径.
- 催化剂负荷和试剂度的系统变化.
主要成果:
- 一个酸复合物被确定为在酸化过程中持久的静止状态.
- 在β-胺-中进行四次替代阻碍了脱碳化.
- 迁移性插入是限制营业额和决定选择性的步骤.
- 只有当化的度接近于零时,化的循环化才具有竞争力.
- 将催化剂负荷从20mol%降低到0.5%将选择性从96%提高到~100%.
结论:
- 反应机制涉及竞争的酸和循环三聚化途径.
- 催化剂加载通过控制自由的可用性而对选择性产生重大影响.
- 优化条件使得水酸化产品在克尺度上以最小的浪费量进行合成.
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