通过 dearomative spirocyclization 来电化学合成酸化的阿扎斯皮罗[4.5]di/trienones 通过 dearomative spirocyclization 来进行这种合成
Xiaocong Zhou1, Jian Wang1, Dumei Ma2
1Institute of Drug Discovery Technology, Ningbo University, Zhejiang, China. wuju@nbu.edu.cn.
概括
这项研究引入了一种新的电化学方法,用于合成使用Cp2Fe.Fe的酸化阿扎斯皮罗[4.5]di/三烯. 这种方法避免了恶劣的条件,并为创建这些复杂分子提供了新的途径.
科学领域:
- 有机合成 有机合成
- 电化学 电化学 电化学
- 药用化学 医学化学
背景情况:
- 阿扎斯皮罗[4.5]di/trienones是药物化学中的重要支架.
- 现有的合成方法通常需要恶劣的条件或缺乏效率.
研究的目的:
- 开发一种新,高效和温和的电化学方法,用于合成化阿扎斯皮罗[4.5]di/trienones.
- 探索开发的方法的范围和 diastereoselectivity.
- 为了阐明反应机制.
主要方法:
- 通过Cp2Fe介导的电化学合成.
- 亲爱的化循环.
- 机械学研究.
主要成果:
- 用广泛的基质范围合成了多种多样化的酸化阿扎斯皮罗[4.5]di/trienones.
- 该方法表现出良好的 diastereoselectivity. 这一方法显示出良好的 diastereoselectivity.
- 这是该类化合物的第一个电化学合成,避免了外部氧化剂和高温.
结论:
- 开发的电化学方法提供了一个简单而有效的途径,以化阿扎斯皮罗[4.5]di/trienones.
- 反应通过激素启动的 dearomative 循环机制进行.
- 这项工作扩大了合成工具箱,以获取有价值的螺旋环化合物.
相关概念视频
Thermal and Photochemical Electrocyclic Reactions: Overview
2.3K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.3K
Thermal Electrocyclic Reactions: Stereochemistry
2.0K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.0K
Photochemical Electrocyclic Reactions: Stereochemistry
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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
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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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Aryldiazonium Salts to Azo Dyes: Diazo Coupling
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The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the...
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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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