内分子辅助交叉合反应:一般合成含有1,3-cis-cis二烯单元的中型环
Scott E Denmark1, Shyh-Ming Yang
1Roger Adams Laboratory, Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
Journal of the American Chemical Society
|March 7, 2002
概括
一种新的合成策略结合了环闭转化和催化合,以有效地创建含有二烯单元的中型环. 这种方法为合成复杂的循环有机分子提供了一个强大的新途径.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 催化剂是一种催化剂.
背景情况:
- 建造中型环 (9-12个成员) 仍然是一个综合性挑战.
- 现有的方法往往缺乏对复杂结构的效率或广泛适用性.
研究的目的:
- 开发一种新且有效的合成中型环的方法.
- 将一个内部的1,3-cis-cis-diene单元纳入目标环.
- 探索新合成方法的范围和局限性.
主要方法:
- 采用了聚催化环闭甲解 (RCM) 和催化,辅助的分子内交叉合的组合.
- 带有Z-iodoalkenyl结合物的醇被化并经过RCM处理,形成不和醇.
- 用四甲基化物和[allylPdCl](2) 激活西洛,用于随后的环闭反应.
主要成果:
- 成功合成了含有1,3-cis-cis二烯单元的9,10,11和12个环.
- 在环闭反应中取得了高产量.
- 扩展了合成9个环不和乙烯的方法.
- 证明了一种高度立体特异的分子内合过程.
结论:
- 开发的方法提供了一种有效和强大的途径,用于构建具有内部二烯单元的中型环.
- 该过程在基组的定位上提供了灵活性,并有可能合成各种碳循环和异环.
相关概念视频
Disubstituted Cyclohexanes: cis-trans Isomerism
Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers.
In cyclohexane, the substituents can occupy different positions generating distinct isomers.
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.
Stability of Conjugated Dienes
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Radical Reactivity: Intramolecular vs Intermolecular
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak carbon–halogen...
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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...

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