一种独特的压力驱动循环艾伦反应模式:向中央艾伦碳原子的群体迁移
1Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, United States.
Journal of the American Chemical Society
|April 22, 2023
概括
循环亚伦可以通过新的群迁移策略转化为替代的. 这种方法克服了传统反应的局限性,使复杂分子合成成为可能.
科学领域:
- 有机化学
- 合成化学
背景情况:
- 压力循环亚伦是高度反应的中间体.
- 1,2,4-环三烯是通过四-尔斯-阿尔德反应生成的环二烯的子类.
- 一个关键的限制是它们倾向于异构成类.
研究的目的:
- 开发替代的新合成途径.
- 为了克服循环基的异构化限制.
- 在循环烯化学中探索醇乙烯和醇的新型反应性.
主要方法:
- 从带有基的1,3-基生成1,2,4-基基.
- 用乙醇乙烯或乙醇乙烯修改enyne成分.
- 实验研究和密度函数理论 (DFT) 的计算.
主要成果:
- 乙醇乙烯或乙醇改导组迁移 (或乙烯) 而不是迁移.
- 这种新型的反应性导致形成高度替代的产物,如基.
- 组迁移发生在从氧原子到中央的碳中.
结论:
- 已经建立了一种新方法来从循环亚伦中合成替代.
- 这一策略有效地控制了循环基的反应性,防止不必要的异构化.
- 这些发现为在有机合成中引入分子复杂性提供了有价值的工具.
相关概念视频
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
2.8K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
2.8K
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
2.2K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
2.2K
Stability of Substituted Cyclohexanes
12.7K
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
12.7K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
6.2K
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...
6.2K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
14.5K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
14.5K
Halogenation of Alkenes
16.0K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
16.0K


![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)