终端基因与基醇的Pd(0) 催化直接脱水合,以获得1,4-基因
Yang-Xiong Li1, Qing-Qing Xuan, Li Liu
1Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Journal of the American Chemical Society
|August 17, 2013
概括
一个新的催化系统使得和醇的直接合能够形成1,4-. 这种催化反应提供了一种具有广泛功能组耐受性的多功能合成途径.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 1,4-类是有机合成中有价值的构建模块.
- 现有的合成1,4-的方法往往涉及多个步骤或恶劣的条件.
研究的目的:
- 开发一种直接且高效的合成1,4-氨酸的方法.
- 探索一种用于脱水合的新型催化系统.
主要方法:
- 终端基与基醇的直接脱水合.
- 使用Palladium tetrakis ((triphenylphosphine) [Pd ((PPh3) 4) 和一个N,P-连接体的催化.
- 来自 (IV) 异氧化物 (Ti (OiPr) 4) 的帮助.
主要成果:
- 通过直接合成功合成了1,4-enynes.
- 反应表明对广泛的功能群的耐受性.
- 有效的是Pd(PPh3) 4和N,P-连接体系统与Ti(OiPr) 4.
结论:
- 已经建立了一个新的合成路径到1,4-enynes.
- 开发的方法是有机合成的宝贵工具.
- 催化系统提供了效率和功能组兼容性.
相关概念视频
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.
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.
Acid-Catalyzed Dehydration of Alcohols to Alkenes
In a dehydration reaction, a hydroxyl group in an alcohol is eliminated along with the hydrogen from an adjacent carbon. Here, the products are an alkene and a molecule of water. Dehydration of alcohols is generally achieved by heating in the presence of an acid catalyst. While the dehydration of primary alcohols requires high temperatures and acid concentrations, secondary and tertiary alcohols can lose a water molecule under relatively mild conditions.
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.
Preparation of Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.

