易于将二烯转化为循环烯异构体:意想不到的C-N和C-H键裂变
Yuzhong Wang1, Hunter P Hickox1, Yaoming Xie1
1Department of Chemistry and the Center for Computational Chemistry, The University of Georgia , Athens, Georgia 30602-2556, United States.
Journal of the American Chemical Society
|November 2, 2017
概括
研究人员从酸盐和二二烯的反应中合成了新型基和循环基. 溶剂的选择影响了产品的分布,产生了不同的环结构.
科学领域:
- 有机化学
- 主要组化学
- 基化合物
背景情况:
- 碳稳定化合物具有独特的反应性.
- 了解新环系统的形成途径至关重要.
研究的目的:
- 研究硫酸盐与碳稳定型二二烯的反应.
- 描述由此产生的zwitterionic和循环烯产品.
- 探索溶剂对反应结果和产品选择性的影响.
主要方法:
- 硫酸盐 (1) 与二二二烯 (2) 在四水 (THF) 和多中发生反应.
- 隔离和表征五个成员的zwitterionic烯 (3) 和四个成员的循环烯 (4).
- 在同位素产品3和4中探测结合的实验和理论方法.
主要成果:
- 在THF中反应出乎意料地产生了zwitterionic烯 (3) 和循环烯 (4).
- 产品3通过插入伊米达C-H键而形成,而产品4通过插入N键而形成.
- 在中发生反应,主要产生基烯 (3).
结论:
- 这项研究报告了首次合成含硫的五个基环.
- 溶剂的极性对反应途径和产品的分布有重大影响.
- 通过使用补充方法对同位素烯的结合进行了详细的研究.
相关概念视频
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
5.1K
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
5.1K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
6.1K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
6.1K
Cycloaddition Reactions: Overview
3.6K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
3.6K
Stereoisomerism of Cyclic Compounds
11.2K
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
11.2K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
12.7K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
12.7K
Disubstituted Cyclohexanes: cis-trans Isomerism
14.5K
Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
14.5K


![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)