的电化学循环化,以构建五个成员的-异环环
Lifen Peng1, Ting Wang1, Zhiwen Yuan1
1Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201, P. R. China.
Beilstein journal of organic chemistry
|October 22, 2025
概括
类的电化学循环化提供了一种绿色和高效的方法来合成多样化的五环环,这在制药和材料科学中至关重要. 本文重点介绍了使用这些技术构建英多尔,异因多林,罗尔和伊米达的关键方法.
科学领域:
- 有机化学 有机化学
- 电化学 电化学 电化学
- 合成方法论 合成方法论
背景情况:
- 五环环是制药,天然产品和材料科学中的重要支架.
- 类是多用途的构建块,易于获得和反应性的合成物.
- 电化学转化为传统合成方法提供了可持续和高效的替代方案.
研究的目的:
- 审查和突出说明类的电化学循环反应,用于构建五个成员的异环环.
- 为了分类和详细介绍不同五个成员环系统的各种合成策略.
- 讨论这些电化学转换的潜在反应机制.
主要方法:
- 乙烯涉尿素的电化学内分子合用于醇合成.
- 用终端基因对本扎米德进行电化学无效化,以合成异因多利诺.
- 基因的电化学循环化与乳化物用于醇合成.
- 电化学并联 迈克尔添加/亚化/循环化用于伊米达合成.
- 电化学 [3 + 2] 循环添加用于1,2,3-三醇合成.
主要成果:
- 通过各种电化学途径成功地构建了内骨.
- 通过电化学取消和循环的有效合成isoindolinones.
- 使用电化学无效和并联反应形成pyrroles和imidazoles.
- 通过电化学循环添加反应获得伊米达索皮里丁和1,2,3-醇.
结论:
- 基因的电化学循环化提供了一个强大而通用的平台,用于合成多种多样的五个成员的异环.
- 这些方法在效率,可持续性和功能组耐受性方面具有优势.
- 审查的策略使得医疗相关的支架的建设,在各种领域的潜在应用.
相关概念视频
Electrophilic Addition to Alkynes: Halogenation
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Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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Nomenclature of Alkynes
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Alkynes are unsaturated hydrocarbons characterized by the presence of carbon-carbon triple bonds and have a general formula CnH2n-2. The nomenclature of alkynes follows a set of rules similar to alkanes and alkenes; however, alkynes bear the suffix "-yne" instead of "-ane" or "-ene." There are two approaches to naming alkynes:
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Thermal and Photochemical Electrocyclic Reactions: Overview
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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.
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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Preparation of Alkynes: Alkylation Reaction
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Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
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Thermal Electrocyclic Reactions: Stereochemistry
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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.
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