初级离子催化和自催化
Xiang Zhang1, Xiaoyu Hao1, Le Liu1
1Department of Organic Chemistry , University of Geneva , Geneva CH 1211 , Switzerland.
Journal of the American Chemical Society
|December 14, 2018
概括
阳离子-π 相互作用能够在芳表面开启以太循环,显示自催化放大. 这种催化被 π 酸性增强,在富勒伦和产品介导催化上观察到显著的速率增加.
科学领域:
- 有机化学
- 超分子化学
- 材料科学
背景情况:
- 环氧开放循环是有机合成中的基本反应.
- 激活芳香表面用于催化通常需要特定的功能组.
- 非共价相互作用在催化中的作用是一个活跃的研究领域.
研究的目的:
- 在π-酸芳香表面上研究环氧开放循环.
- 探索这些反应中的自催化放大潜力.
- 阐明催化机制,特别是-π相互作用的作用.
主要方法:
- 在各种π酸表面 (,NDI,PDI,富勒) 上对环氧开放的实验研究.
- 动力分析以确定速度增强和催化效率.
- 计算研究 (例如,DFT) 模型反应机制和过渡状态.
主要成果:
- 在没有额外的激活剂的π酸芳香表面上发生环氧化开启.
- 随着芳香系统的内在π酸度增加,催化活性也会增加.
- 观察到显著的速率提升,在烯上的离子催化率高达270倍,自催化率高达5100M-1.
- 在产品存在的情况下,自催化率的增加证实了这一点.
结论:
- 阳离子-π 相互作用是观察到的催化活性的关键.
- 自催化起着重要的作用,由过渡状态和产品之间的键促进.
- 这些发现为设计基于π-酸表面非共价相互作用的高效催化系统开辟了新的途径.
相关概念视频
Catalysis
30.5K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
30.5K
π Molecular Orbitals of the Allyl Cation and Anion
5.5K
An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with...
5.5K
Introduction to Mechanisms of Enzyme Catalysis
10.7K
For many years, scientists thought that enzyme-substrate binding took place in a simple "lock-and-key" fashion. This model stated that the enzyme and substrate fit together perfectly in one instantaneous step. However, current research supports a more refined view scientists call induced fit. The induced-fit model expands upon the lock-and-key model by describing a more dynamic interaction between enzyme and substrate. As the enzyme and substrate come together, their interaction causes...
10.7K
π Molecular Orbitals of 1,3-Butadiene
11.7K
Conjugated dienes have lower heats of hydrogenation than cumulated and isolated dienes, making them more stable. The enhanced stabilization of conjugated systems can be understood from their π molecular orbitals.
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...
11.7K
Aromatic Hydrocarbon Anions: Structural Overview
3.7K
Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH2 group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH2 group is sp3 hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.
Due to the absence of continuous...
Due to the absence of continuous...
3.7K
π Electron Effects on Chemical Shift: Overview
1.7K
An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
1.7K


