在环境条件下在有机微滴中由界面电场驱动的无催化剂激素反应
Jin Luo1, Xulin Gong2, Haobin Ye1
1State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University, Xiamen 361005, China.
Journal of the American Chemical Society
|December 29, 2025
概括
有机微滴中的内在电场驱动了没有催化剂的激进反应. 这项研究证明了使用二甲基硫化物 (DMSO) 微滴的无催化剂甲基化,为有机合成开辟了新的途径.
科学领域:
- 有机化学
- 物理化学
- 化学物理
背景情况:
- 静电场可以驱动化学反应.
- 在有机微滴界面上存在界面电场.
研究的目的:
- 证明有机微滴中的内在界面电场可以在没有外部催化剂或应用潜力的情况下驱动激进反应.
- 通过使用二甲基硫化物 (DMSO) 微滴来研究无催化剂甲基化的机制.
主要方法:
- 诱导电荷积累的测量
- 拉曼光谱学
- 同位素标记
- 螺旋捕获实验
- 密度函数理论 (DFT) 的计算
主要成果:
- 在pyridine-DMSO微滴中证实了强大的界面电场.
- 在环境条件下以21.1μM/h的速度实现了甲二甲的无催化剂甲基化.
- 一个涉及电场诱导的和甲基生成的反应机制被阐明.
结论:
- 有机微滴中的内在界面电场可以有效地驱动激进反应.
- 这一战略为无催化剂的有机合成提供了一种新的方法.
- 这些发现具有各种激素介导的有机反应的广泛潜力.
相关概念视频
Radical Reactivity: Intramolecular vs Intermolecular
2.1K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
2.1K
Radical Reactivity: Overview
2.6K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.6K
Radical Reactivity: Steric Effects
2.4K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
Along with electronic...
2.4K
Radical Reactivity: Electrophilic Radicals
2.4K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
2.4K
Radical Reactivity: Nucleophilic Radicals
2.6K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.6K
Radical Autoxidation
3.0K
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
3.0K


