解读1-(2-乙烯基) -3,3-二甲基三的循环化过程中的机械二分法:围循环和伪甲酸路径之间的竞争
David B Kimball1, Timothy J R Weakley, Rainer Herges
1Department of Chemistry, University of Oregon, Eugene 97403-1253, USA.
Journal of the American Chemical Society
|November 7, 2002
概括
这项研究探讨了 (2-乙烯基) 三的循环化机制. 不同的路径,包括碳和环环路,导致各种产品,如isoindazoles和cinnolines.
科学领域:
- 有机化学 有机化学
- 反应机制 反应机制
背景情况:
- 循环化反应是有机合成的基础.
- 了解反应途径对于控制产品形成至关重要.
研究的目的:
- 为了阐明 (2-乙烯基) 三烯循环的机械路径.
- 为了研究热和铜介导反应条件.
- 为了识别关键的中间体和反应产物.
主要方法:
- 在热和铜介导条件下对 (2-乙烯基) 三的实验研究.
- 密度函数理论 (DFT) 的计算.
- 陷的研究.
主要成果:
- 建议在isoindazole形成过程中采用一条碳路径,其中的中间体易受氧气,二元化或捕获的影响.
- DFT计算支持卡尔形成的伪甲酸盐路径.
- 通过一种zwitterionic dehydrocinnolinium中间体,通过实验性捕捉支持,为诺林的形成提出了一个环周路径.
结论:
- (2-乙烯基) 三的循环化通过不同的机械路径进行,具体取决于条件.
- 碳和环环路决定了不同的异环产品的形成.
- 计算和实验数据为拟议的机制提供了强有力的支持.
相关概念视频
Preparation of Diols and Pinacol Rearrangement
Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Thermal and Photochemical Electrocyclic Reactions: Overview
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.
Thermal Electrocyclic Reactions: Stereochemistry
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.
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
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.
Pericyclic Reactions: Introduction
Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...


