C ((sp3) -F 纽带激活由易斯基-基通过协定的电子-化物转移激活
Xueying Guo1, Yuchen Zhang1, Xiaoyu Lai1
1Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 20032, China.
Angewandte Chemie (International ed. in English)
|October 29, 2024
概括
研究人员开发了一种新方法,使用易斯基-基激素,通过协同的电子-转移机制在醇中选择性激活强碳- (C-F) 键,从而使直接的原子抽象成为可能.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
背景情况:
- 在碳- (C-H) 键较弱的情况下,选择性激活强碳- (C-F) 键是合成化学的一个重大挑战.
- 激素通路通常用于键激活,但由于其高键解离能,C-F键裂变仍然很困难.
研究的目的:
- 研究一种用于在醇中选择性激活C-F键的新型机制.
- 探索易斯基-玻利基激素在促进C-F键裂解中的潜力.
- 扩大素原子转移反应的范围.
主要方法:
- 用密度函数理论 (DFT) 的计算来研究反应机制.
- 研究了易斯基-玻利基与醇基的反应性.
- 提出并分析了一种协调的电子-化物转移机制.
主要成果:
- 一个新的协同的电子化物转移机制被披露用于C-F键激活.
- 易斯基基激素被证明可以选择性地激活C-F债券而不是C-H债券.
- 该机制可以直接抽取原子,产生基基.
结论:
- 开发的机制为选择性C-F债券激活提供了一个新的策略.
- 这种方法扩大了在有机化学中激素反应的实用性.
- 这些发现提供了对C-F债券裂变路径的更深入的理解.
相关概念视频
Hybridization of Atomic Orbitals I
46.6K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
46.6K
Radical Formation: Addition
1.7K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
1.7K
Radical Formation: Homolysis
3.5K
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
3.5K
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
5.8K
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.
5.8K
Radical Formation: Overview
2.1K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.1K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
1.8K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
1.8K


