基于BINAP的坚固,有机和多孔的金属有机框架用于高度反选择性的循环反应
Takahiro Sawano1, Nathan C Thacker1, Zekai Lin1
1Department of Chemistry, University of Chicago , 929 E. 57th Street, Chicago, Illinois 60637, United States.
基于BINAP的新金属有机框架 (MOF) 与 (Rh) 功能化,作为不对称循环的高度反选择性固体催化剂. 与同质催化剂相比,这些MOF催化剂的活性和可回收性有所改善.
科学领域:
- 材料科学
- 催化剂
- 有机化学
背景情况:
- 金属有机框架 (MOF) 为催化提供可调节的多孔结构.
- 不对称的催化剂需要高度选择性和活跃的催化剂.
- 奇拉BINAP连接体对于选择性转化至关重要.
研究的目的:
- 设计和合成基于BINAP的MOF用于不对称的催化.
- 研究Rh金属化MOF在循环反应中的性能.
- 探索MOF结构对催化活性和选择性的影响.
主要方法:
- 基于BINAP的Zr-MOF (BINAP-MOF和BINAP-dMOF) 的合成与UIO拓.
- MOFs与复合物的合成后化.
- 在不对称的还原循环化,阿尔德烯循环异构化和Pauson-Khand反应中进行催化评估.
- 与同质催化剂进行比较.
主要成果:
- 具有Rh功能化的BINAP-MOF有效地催化了1,6-氨酸的反反选择性循环,其反反度过多 (高达99% ee).
- 由于隔离位置,MOF催化剂的活性明显高于同质对照剂 (4-7倍).
- 在BINAP-dMOF中,混合连接器策略创建了一个更开放的结构,使得硬质要求较高的Pauson-Khand反应的催化成为可能.
- 具有Rh功能的BINAP- dMOF可以在没有性能损失的情况下回收.
结论:
- 基于BINAP的MOF作为坚固,可回收和高度反选择性的单位固体催化剂.
- 在MOF中使用混合连接剂的方法可以增强固体阻碍反应的催化性能.
- 这项工作扩大了MOF在不对称催化中的实用性,比同质系统提供了优势.
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