用烯酸试剂对酒精进行循环化
Zibo Bai1, Beatrice Lansbergen1, Tobias Ritter1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr, Germany.
Journal of the American Chemical Society
|November 27, 2023
概括
这项研究引入了一种新方法,用于合成使用BCP-试剂和双铜/光反氧催化剂的双环[1.1.1] (BCP) 乙烯. 这种基于基的方法避免了不稳定的中间体,使BCP乙烯合成具有广泛的功能群耐受性.
科学领域:
- 有机合成
- 医学化学
- 催化剂
背景情况:
- 自行车[1.1.1] (BCP) 图案因其独特的空间特性而在药物化学中具有价值.
- 现有的BCP合成方法通常涉及恶劣的条件或不稳定的碳酸中间体,限制了它们的范围.
- 在药物发现和开发过程中,开发有效和多用途的BCP组合方法至关重要.
研究的目的:
- 从酒精制成的双环[1.1.1] (BCP) 乙烯的第一个合成方法
- 开发一种可以绕过不稳定的BCP碳酸的催化系统.
- 证明新方法在后期功能化和模拟合成中的实用性.
主要方法:
- 作为BCP来源使用了双环[1.1.1]二试剂.
- 在以太化反应中采用双铜/光电还原催化系统.
- 研究了与初级,二级和三级酒精反应的范围.
主要成果:
- 从各种酒精中成功合成了BCP乙烯.
- 这种由铜介导的激素过程有效地避免了不稳定的BCP碳酸的形成.
- 已证明具有广泛的功能群耐受性,包括在天然产品和药品的后期功能化中的应用.
- 促进了现有药物的BCP类似物的快速合成.
结论:
- 已经开发出一种新且高效的合成BCP乙烯的方法.
- 与传统的基于碳酸的方法相比,介导基路提供了显著的优势.
- 这种方法为药物化学家提供了强大的工具,使其能够获得含有BCP的新化合物,并促进药物发现.
相关概念视频
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
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.
1.9K
Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
3.5K
The Wittig reaction, which converts aldehydes or ketones to alkenes using phosphorus ylides, proceeds through a nucleophilic addition‒elimination process.
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
3.5K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.1K
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.
18.1K
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
7.8K
The Wittig reaction is the conversion of carbonyl compounds-aldehydes and ketones-to alkenes using phosphorus ylides, or the Wittig reagent. The reaction was pioneered by Prof. Georg Wittig, for which he was awarded the Nobel Prize in Chemistry.
7.8K
Preparation of Alcohols via Addition Reactions
6.3K
Overview
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
6.3K
Preparation of Alkynes: Alkylation Reaction
10.2K
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.
10.2K


