一个氧化[2,3]-sigmatropic重新排列的基化物
Benjamin F Strick1, Devon A Mundal, Regan J Thomson
1Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
Journal of the American Chemical Society
|August 23, 2011
概括
研究人员开发了一种高效的氧化[2,3]-sigmatropic重组,用单片N-烯中间体对基化物进行重组. 这种新的方法通过平稳的转化提供了获取有价值的化合物前体的机会.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 反应机制 反应机制
背景情况:
- 基化物是多功能合成中间体.
- 西格马特罗普重组是强大的碳-碳键形成反应.
- 开发新的合成路径对于有机合成至关重要.
研究的目的:
- 报告一个有效的氧化[2,3]-sigmatropic重新安排的基化物.
- 研究涉及单片N-二烯中间体的机制.
- 证明产品作为各种化合物的前体的实用性.
主要方法:
- 制备基化前体.
- 氧化使用酸来诱导重新排列.
- 由此产生的产品的特征.
主要成果:
- 实现了一种有效的氧化[2,3]-sigmatropic重排.
- 在温和的条件下,反应进展顺利.
- 这些产品是进一步化学转换的有价值的合成子.
结论:
- 已经建立了一个新的和高效的合成路线到功能化化合物.
- 氧化[2,3]-sigmatropic重组为有机化学家提供了一个新的工具.
- 该方法提供了对各种分子架构的访问.
相关概念视频
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
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.
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
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.
Thermal Sigmatropic Reactions: Overview
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.

