由α-基基子衍生出的基基的循环化
Jingwei Li1, Chunrui Sun, Daesung Lee
1Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA.
Journal of the American Chemical Society
|April 24, 2010
概括
研究人员开发了一种新的循环化反应,使用基基二甲. 这种方法选择性地插入到碳-键中,为有机化学提供了一条新的合成途径.
科学领域:
- 有机化学 有机化学
- 有机化学 有机化学
- 合成方法论 合成方法论
背景情况:
- 循环化反应是有机合成的基础.
- 基利丁碳是多用途的中间体.
- 控制碳酸插入反应的选择性仍然是一个挑战.
研究的目的:
- 为了开发一种新的循环化反应.
- 为了研究从α-基中衍生出的基基的反应性.
- 了解控制碳烯插入选择性的因素.
主要方法:
- 从α-基基生成基基的生成.
- 碳与基质的反应形成环烯.
- 对反应产物的分析以确定选择性.
主要成果:
- 开发了一种新的循环化反应,涉及Calpha-Si键插入.
- 该反应对Cgamma-H插入或添加不和键的卡尔法-Si键插入表现出极好的选择性.
- 发现绳索中的α-氧促进了Cgamma-H插入,但Calpha-Si插入仍然具有竞争力.
结论:
- 开发的循环化反应为通过calpha-si键插入形成循环的新途径提供了新的途径.
- 这项研究突出了α-基衍生碳的独特反应性.
- 了解选择性因素为设计未来合成策略提供了洞察力.
相关概念视频
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
[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.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
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.
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.


