一个前所未有的形式 [5 + 2] 循环添加与o-碳素通过Tandem [3 + 2] 循环添加/氧气迁移/芳香化序列
Da Zhao1, Jiji Zhang1, Zuowei Xie1
1Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong , Shatin, N. T., Hong Kong, Hong Kong, China.
Journal of the American Chemical Society
|October 16, 2015
概括
研究人员开发了和o-carborynes之间的新形式的 [5 + 2] 循环添加反应. 这种方法有效地合成了复杂的碳酸融合的七个成员的异环,扩展了合成化学.
科学领域:
- 有机化学
- 医学化学
- 材料科学
背景情况:
- 异环化合物是天然产品和制药中的关键支架.
- 循环添加反应提供了复杂分子结构的有效途径.
- 碳酸是一种独特的含化合物,具有多种应用.
研究的目的:
- 报告一种新的合成方法,用于制造碳融合的异环.
- 在循环添加反应中探索o-carborynes的反应性.
- 调查新碳酸循环添加的机制.
主要方法:
- 尼和o-carborynes之间的正式 [5 + 2] 循环添加反应.
- 包括反应优化和产品表征在内的实验研究.
- 计算分析 (例如,DFT计算) 来阐明反应机制.
主要成果:
- 成功合成了碳酸融合的七个成员的异态环.
- 一种涉及 [3 + 2] 循环添加,N-O 键裂变,氧迁移和重新芳香化的反应途径的鉴定.
- 作为五原子合成体的子部分的演示,包括两种异质原子.
结论:
- 已经建立了一个新的,前所未有的正式 [5 + 2] 循环加法.
- 开发的方法提供了独特的含有碳酸的异环结构.
- 这项研究为和碳素的化学行为提供了新的见解.
相关概念视频
Cycloaddition Reactions: Overview
3.8K
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.
3.8K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
13.7K
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.
13.7K
Nitrosation of Enols
10.6K
The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
10.6K
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
3.1K
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).
3.1K
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
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
5.9K
α,β-Unsaturated carbonyl compounds are molecules bearing a carbonyl and alkene functionality in conjugation with each other. The conjugation in the molecule leads to three resonance structures. The hybrid form exhibits two probable electrophilic sites: the carbonyl carbon and the β carbon.
5.9K

![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)
