一旦分裂的C-C键被改造:可逆的C-C键裂解二丁化合物的复合物
Tamotsu Takahashi1, Zhiyi Song, Yi-Fang Hsieh
1Catalysis Research Center and Graduate School of Life Sciences, Hokkaido University, and SORST, Japan Science and Technology Agency, Kita-ku, Sapporo 001-0021, Japan. Tamotsu@cat.hokudai.ac.jp
Journal of the American Chemical Society
|October 28, 2008
概括
研究人员发现,Cp部分的裂开的碳-碳键可以重新组合,形成印丁产物. 此外,还提出了这种碳-碳键裂变的新机制.
科学领域:
- 有机化学 有机化学
- 有机金属化学 有机金属化学
背景情况:
- 环丁 (Cp) 连接体在有机金属化学中至关重要.
- 了解Cp-金属复合物的反应性和转变对于催化和材料科学至关重要.
研究的目的:
- 为了研究Cp部分中裂开的碳-碳键的重组.
- 阐明一种用于在有机金属复合体中Cp部分的碳-碳键的裂解的新型机制.
主要方法:
- 对有机金属复合物的反应监测.
- 使用光谱技术进行产品表征.
- 机械学研究涉及运动分析和计算建模.
主要成果:
- 观察到复合体2中Cp部分的裂开的碳-碳键重新组合.
- 通过这种重组途径成功合成了印丁产品.
- 提出了一种解释Cp部分碳-碳键裂变的新机制,并得到实验证据的支持.
结论:
- 这项研究表明了Cp部分中碳-碳键重组的潜力,从而导致印丁形成.
- 拟议的新型机制为有机金属化学中的Cp配体的反应性提供了新的见解.
相关概念视频
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
Radical Formation: Homolysis
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
C–C Bond Cleavage: Retro-Aldol Reaction
The reverse of the aldol addition reaction is called the retro-aldol reaction. Here, the carbon–carbon bond in the aldol product is cleaved under acidic or basic conditions to form two molecules of carbonyl compounds. The mechanism of the reaction consists of three steps.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
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.
Alkynes to Carboxylic Acids: Oxidative Cleavage
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions generating free carboxylic acid...


