调整基于黄素的光敏剂,以实现基胺的高效光氧化合
Huimin Guo1, Yang Qiu1, Siyu Liu1
1School of Chemistry, Dalian University of Technology, No. 2, Linggong Road, Dalian, 116024, P. R. China. guohm@dlut.edu.cn.
Physical chemistry chemical physics : PCCP
|December 12, 2023
概括
基于黄素的敏感剂有效地利用氧和可见光催化来自胺的绿色合成imines. 化黄素,特别是DB-FL,在这种光氧化合反应中表现出卓越的性能.
科学领域:
- 有机化学 有机化学
- 光催化作用的光催化
- 绿色化学 绿色化学
背景情况:
- 胺是重要的合成中间体.
- 传统的胺基合成方法通常涉及恶劣的条件或有毒的试剂.
- 开发可持续和高效的催化系统用于胺基合成是非常理想的.
研究的目的:
- 探索基于黄素的敏化剂 (FLPSs) 用于基胺与伊胺的光氧化合.
- 调查化学功能化对黄素光物理性质和催化性能的影响.
- 为了阐明光催化反应的机制.
主要方法:
- 弗拉敏感剂 (FL,MB-FL,DB-FL,Ph-FL) 的合成和表征.
- 光物理性能测量 (吸收,量子产量,三倍寿命).
- 基胺在可见光照射下与O2进行光氧化合反应.
- 实验和理论机理学研究.
主要成果:
- 黄素与和基的化学功能化增强了它们的光物理性质.
- DB-FL 显示出优越的催化活性和对 imine 合成的选择性.
- 在温和的条件下,DB-FL使得基胺在温和条件下高转化率转化为胺.
- 机械学研究揭示了电子转移在催化循环中的主导作用.
结论:
- 基于flavin的敏感剂是绿色 imine合成的有效光催化剂.
- DB-FL 是一种高效的光催化剂,用于从基胺中合成因胺.
- 这项工作提供了对用于有机合成的新型光催化剂设计的见解.
相关概念视频
Oxidation of Phenols to Quinones
3.1K
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
3.1K
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
2.9K
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the...
2.9K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.1K
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
6.0K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
6.0K
Reactions at the Benzylic Position: Oxidation and Reduction
3.7K
The benzylic position describes the position of a carbon atom attached directly to a benzene ring. Benzene by itself does not undergo oxidation. In contrast, the benzylic carbon is quite reactive in the presence of strong oxidizing agents such as KMnO4 or H2CrO4. Therefore, alkylbenzenes are readily oxidized to benzoic acid, irrespective of the type of alkyl groups.
3.7K
![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
