涉及二转化[12] 无核的反应
Matthew K Kiesewetter1, Matthew N Gard, Richard C Reiter
1Department of Chemistry, Illinois State University, Normal, Illinois 61790-4160, USA.
Journal of the American Chemical Society
|December 7, 2006
概括
研究人员通过脱化和环闭反应合成了新的anulene衍生物. 这些发现促进了对复杂的多环芳化合物形成和反应性的理解.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 聚环芳香碳化合物 聚环芳香碳化合物
背景情况:
- 无烯是带有联双键的循环碳化合物.
- 复杂的多环系统的合成仍然是有机化学的一个挑战.
研究的目的:
- 探索新型合成路径,以复杂的anulene衍生物.
- 为了研究 [12]annulene前体的化环系统的形成.
主要方法:
- 使用三氧化物低温脱化的pentabromocyclododecene.
- [12]烯与三氧化和18-皇冠-6.6的反应.
- 氧化和还原步骤以分离中性和极端物种.
主要成果:
- 来自pentabromocyclododecene的11,12-dihydro-[8]annuleno-[6]annulene的阳离子基的形成.
- 隔离了11,12-dihydro-[8]annuleno-[6]annulene的中性分子.
- 来自 [12]annulene 前体的 heptalene 离子基的合成.
结论:
- [12]烯的1,7-di-trans同位素是肝烯离子基的前体.
- 这项研究表明了构建化多环芳香系统的新途径.
相关概念视频
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
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.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
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.
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.
Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia
Alkynes can be reduced to trans-alkenes using sodium or lithium in liquid ammonia. The reaction, known as dissolving metal reduction, proceeds with an anti addition of hydrogen across the carbon–carbon triple bond to form the trans product. Since ammonia exists as a gas (bp = −33°C) at room temperature, the reaction is carried out at low temperatures using a mixture of dry ice (sublimes at −78°C) and acetone.
When dissolved in liquid ammonia, an alkali metal, such as sodium, dissociates into a...
When dissolved in liquid ammonia, an alkali metal, such as sodium, dissociates into a...
Photochemical Electrocyclic Reactions: Stereochemistry
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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