用Pd(II) 催化剂激活基激活的甲C(sp3) -H键
Masayuki Wasa1, Kelvin S L Chan, Xing-Guo Zhang
1Department of Chemistry, The Scripps Research Institute, La Jolla, California 92037, United States.
Journal of the American Chemical Society
|November 3, 2012
概括
研究人员开发了一种新的催化方法,用于C-H键的功能化. 这种方法有效地将基组安装在胺上,使用专门的氨酸连接体.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 药用化学 医学化学
背景情况:
- 催化C-H激活是有机合成中的一个强大的工具.
- 对于C ((sp ((3)) -H债券的功能化,特别是对胺的功能化,仍然具有挑战性.
- 开发用于C-H功能化的选择性和高效的方法对于药物发现和材料科学至关重要.
研究的目的:
- 开发一种新的催化方法,用于胺中β-甲基C(sp(3)) -H键的直接化.
- 探索连接体设计在实现选择性C-H激活中的作用.
- 为了证明开发的方法对各种非循环和循环胺的广泛适用性.
主要方法:
- 使用的 ((II) 催化.
- 采用相互排斥和富含电子的林连接体来指导C-H激活.
- 研究了连接体调整以优化反应条件和基质范围.
- 将该方法应用于各种非循环和循环胺基质.
主要成果:
- 实现了有效的Pd(II) 插入到β-甲基C(sp(3)) -H键中.
- 在温和条件下证明了胺的成功合.
- 确定了一种特定的氨酸配体,促进了高反应性和选择性.
- 展示了该方法在各种胺结构上的有效性.
结论:
- 开发的方法为在胺中具有挑战性的C ((sp ((3)) -H键的功能化提供了一条新途径.
- 量身定制的素连接体是催化阿里化成功的关键.
- 这种方法有可能简化复杂分子和候选药物的合成.
更多相关视频
相关概念视频
Metal-Ligand Bonds
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...
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
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.
Cationic Chain-Growth Polymerization: Mechanism
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...
Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)

