在具有特权的二基共价有机框架中构建单-金属复合体,用于催化不对称化
Zehao Zheng1, Chen Yuan1, Meng Sun1
1School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
Journal of the American Chemical Society
|March 10, 2023
概括
在共价有机框架 (COF) 中固定的基单金属催化剂可实现高效的非对称化. 这些特权基异质催化剂在温和条件下提供了卓越的性能和可回收性.
科学领域:
- 有机金属化学
- 材料科学
- 催化剂
背景情况:
- 有特权的二素配体形成稳定的金属复合物,对催化至关重要.
- 由于可能对单金属复合物进行重新排列,催化剂活性往往不清楚.
研究的目的:
- 在共价有机框架 (COF) 中构建奇拉单金属复合体.
- 评估它们作为非对称化的单位异质催化剂的有效性.
主要方法:
- 通过用二胺凝结四纯MeO-BIPHEP合成同体二维COF.
- 通过COF的合成后化制备的单位Ir/Ru-单催化剂.
- 测试的催化剂在素和β-基的不对称化.
主要成果:
- 在不对称化中达到高达99.9%的反体过量.
- 证明了COF支持的催化剂的优良催化活性和可回收性.
- 由于COF的多孔性,可以在环境/中等压下进行反应.
结论:
- 双氨酸的单金属复合物是不对称化的活性中心.
- 开发了一种用于制备特权基异质催化剂的新方法.
- COF固定为单位催化剂设计和应用提供了强大的平台.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.4K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.9K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
7.9K
Reduction of Alkenes: Catalytic Hydrogenation
12.3K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
12.3K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.6K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.6K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
10.3K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
10.3K
Electrophilic Addition to Alkynes: Halogenation
8.4K
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
8.4K


