终端类的Ru催化循环转化为循环类
Jesús A Varela1, Carlos González-Rodríguez, Silvia G Rubín
1Departamento de Química Organica y Unidad Asociada al CSIC, Facultad de Química, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
Journal of the American Chemical Society
|July 27, 2006
概括
一种新型的催化反应有效地从终端类化合物合成环基. 这种方法还允许循环异构化到合性化物,这两种方法都涉及催化乙烯化物.
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:
- 终端类是有机合成中的多功能前体.
- 催化剂以调解各种有机转化而闻名.
研究的目的:
- 开发一种高效的合成环基的方法.
- 在催化下探索终端类的反应性.
主要方法:
- 终端类的鲁催化循环.
- 研究反应条件以控制产品的形成.
主要成果:
- 实现了循环烯的有效制备.
- 在特定的条件下观察到循环异构化为合性化物.
- 这两种转化都通过催化乙烯中间体进行.
结论:
- 已经建立了一个新的Ru催化路径,从终端类化合物到循环类化合物.
- 催化系统表现出多功能性,使得可以获得循环基和合化物.
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.
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.
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Introduction
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
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.
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...
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.

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