在扩展的viologen-based旋风中的合作反应
Edward J Dale1, Daniel P Ferris1, Nicolaas A Vermeulen1
1Department of Chemistry, Northwestern University , Evanston, Illinois 60208, United States.
Journal of the American Chemical Society
|February 25, 2016
概括
合成了一种具有两个反应性基团的新型四化旋. 这种分子经历了快速的循环添加反应,由于其刚性结构,表现出增强的反应性和并联级联的行为.
科学领域:
- 有机化学
- 超分子化学
- 材料科学
背景情况:
- 基于的环是超分子化学中的多功能支架.
- 基是各种化学转换的关键功能组,包括循环添加.
- 循环系统中的应变和电子效应可以显著影响反应性.
研究的目的:
- 合成一种具有两种基功能的新型四化旋.
- 在循环添加反应中研究旋基的反应性.
- 在刚性旋框架内探索串联级联反应的潜力.
主要方法:
- 一种基于四度的旋的合成.
- 使用二烯和亚的循环添加反应.
- 使用 (1) H NMR 光谱进行表征.
- 分子建模以分析反应能量场景.
主要成果:
- 一个盒状四基旋与两个并置基的成功合成.
- 类在循环添加中表现出高反应性,比非循环类类似物更快.
- 没有观察到稳定的单功能中间体;只检测到起始材料和双功能产品.
- 分子建模表明第二个循环添加的动力障碍较低,有利于双重反应.
结论:
- 合成的旋可以进行高效的循环添加反应.
- 刚性结构促进了并联级联反应,其中第一个反应增强了第二个基的反应性.
- 这项工作突出了压力较大,缺电子的旋对于受控化学转换的有用性.
相关概念视频
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.9K
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.
2.9K
Cycloaddition Reactions: MO Requirements for Thermal Activation
5.1K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
5.1K
Cycloaddition Reactions: Overview
3.7K
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.
3.7K
Stability of Substituted Cyclohexanes
17.2K
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...
17.2K
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
3.0K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
3.0K
Lytic Cycle of Bacteriophages
79.9K
Bacteriophages, also known as phages, are specialized viruses that infect bacteria. A key characteristic of phages is their distinctive “head-tail” morphology. A phage begins the infection process (i.e., lytic cycle) by attaching to the outside of a bacterial cell. Attachment is accomplished via proteins in the phage tail that bind to specific receptor proteins on the outer surface of the bacterium. The tail injects the phage’s DNA genome into the bacterial cytoplasm. In the...
79.9K


