5,6-不被替代的1,4-二皮里丁在Huisgen的1,4-二倍体循环添加和形式的 [2 + 2] 循环添加中的独特反应性
Xiu-Yu Chen1, Hui Zheng1, Ying Han1
1College of Chemistry & Chemical Engineering, Yangzhou University, Jiangsu, Yangzhou 225002, China.
Beilstein journal of organic chemistry
|July 5, 2023
概括
这项研究详细介绍了异类素和二类素的新反应. 新的化异环化合物,伊索奎诺林[1,2-f][1,6]纳二和阿扎比环[4.2.0]八二烯,被高效合成.
科学领域:
- 有机化学 有机化学
- 异环化学 异环化学
- 合成方法论 合成方法论
背景情况:
- 异诺林和1,4-二二胺是重要的异环基架.
- 开发高效的合成路径,以复杂的化异环是有机化学的一个关键挑战.
研究的目的:
- 探索异类素,基乙烯基碳酸盐和1,4-二二胺之间新鲜的反应性.
- 合成新型功能化异诺[1,2-f][1,6]甲胺和相关的融合系统.
主要方法:
- 这是一种三组分反应,涉及异诺林,基乙烯基碳酸盐和5,6-不被替代的1,4-二二.
- 在不同的条件下进行正式的 [2 + 2] 循环添加反应.
主要成果:
- 三组分反应产生了功能化异诺[1,2-f][1,6]纳二素,产量很好,具有很高的二选择性.
- 循环添加反应产生了独特的2-azabicyclo[4.2.0]octa-3,7-dienes作为主要产品和四cyclopenta[b]pyrroles作为次要产品.
结论:
- 已经建立了一种新且高效的合成策略,用于构建复杂的化含杂环.
- 反应条件决定了不同的异环结构的形成,展示了多功能合成潜力.
相关概念视频
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
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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.
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Cycloaddition Reactions: Overview
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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.
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Cycloaddition Reactions: MO Requirements for Thermal Activation
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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.
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Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
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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.
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Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
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Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
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[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
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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.
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