通过基拉尔 (P,N) - 连接物启动的反氧催化
Chetan C Chintawar1, Vivek W Bhoyare1, Manoj V Mane2,3,4
1Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462 066, India.
Journal of the American Chemical Society
|April 18, 2022
概括
这项研究引入了使用新奇的性联体合成有价值的化合物的选性黄金催化. 该方法实现了高产量和抗选择性,为重要的药物中间体提供了一条新途径.
科学领域:
- 有机金属化学
- 不对称的催化
- 医学化学
背景情况:
- 黄金催化是一种有机合成的强大工具.
- 基拉对实现反选择性至关重要.
- 在医学上重要的化合物中常见的Chroman支架.
研究的目的:
- 开发一种新型的选性黄金 (I) /黄金 (III) 反氧催化剂.
- 合成具有医学意义的3氧和3氨基染色体.
- 调查反选择性的机制.
主要方法:
- 设计和合成一种新的血性 (P,N) 连接体 (ChetPhos).
- 催化剂在1,2-氧化和1,2-氨基化中应用.
- 密度功能理论 (DFT) 研究以阐明反应机制.
主要成果:
- 开发的催化系统实现了高产率 (高达88%) 和优异的反选择性 (高达99% ee).
- 对3氧和3氨基染色体的直接接入已经确定.
- DFT研究确定了对抗决定性步骤和联体的电子性质的作用.
结论:
- 这种新型的ChetPhos配体能够实现前所未有的反选择性Au (I) /Au (III) 氧化还原催化.
- 这种方法提供了一条有效的途径,以获得有价值的性衍生物.
- 机械的洞察力有助于合理设计未来的不对称黄金催化剂.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.5K
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...
3.5K
Metal-Ligand Bonds
21.6K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
21.6K
Complexation Equilibria: The Chelate Effect
702
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
702
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.9K
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.
10.9K
EDTA: Chemistry and Properties
2.3K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
2.3K
Complexometric Titration: Ligands
1.1K
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
1.1K


