阿扎普拉达环丁的合成和反应性
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
Journal of the American Chemical Society
|November 30, 2006
概括
N-Sulfonyl阿齐里丁与反应,形成新的双循环复合物. 这些化合物可以进一步功能化,在有机金属化学中提供新的途径.
科学领域:
- 有机金属化学 有机金属化学
- 合成有机化学 合成有机化学
背景情况:
- 的催化对于C-C和C-异原子键的形成至关重要.
- 亚齐里丁是多功能的三分子异环,用于有机合成.
研究的目的:
- 为了研究N-硫нил亚齐里丁与 ((0)) 复合物的活性.
- 探索新型有机中间体的形成及其随后的转化.
主要方法:
- 在现场生成使用Pd2(dba) 3和1,10-phenanthroline.0) 的复合体.
- 氧化性添加N-硫尼尔亚齐里丁到上
- 由铜 (I) 化物促进的分子内碳化.
- 标记研究以阐明反应机制.
- 使用铜(II) 化物对C-Pd键的氧化功能化.
主要成果:
- N-硫乙二烯酸经过氧化添加到中,以产生阿扎帕拉达旋中间体.
- 这些中间体的内分子碳化导致了阿扎帕拉达双环[3.2.1]octanes.octanes的形成.
- 乳标签证实了SN2型攻击在不太受阻碍的亚齐里丁碳和syn-fashion的插入.
- 双循环复合物可以通过氧化-碳键化学物质进一步功能化.
结论:
- 已经建立了一个从N-硫尼尔亚齐里丁中获得azapalladabicyclo[3.2.1]octanes的新型合成途径.
- 这项研究为催化反应提供了机理性的见解,包括立体化学结果.
- 开发的方法提供了构建复杂分子架构的潜力.
相关概念视频
Preparation of Amides
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
[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.
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...
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
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 para position.
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...


