乙烯乙烯基基多克索隆 (乙烯基EBX):获取凯二氧化乙酸盐
Pierre Palamini1, Julien Borrel1, Maël Djaïd1
1Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 4306, 1015 Lausanne, Switzerland.
Organic letters
|October 6, 2023
概括
我们开发了一种新的合成 ketene dithioacetals 使用 thiophenols 和 ethynylbenziodoxolones. 这种方法可以有效地获得功能化衍生物和新型含硫异环.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 凯二乙酸盐是有机合成中的多功能构建块.
- 有效的合成路径对于访问各种功能化衍生品至关重要.
研究的目的:
- 开发一种新且高效的合成凯二酸盐的方法.
- 在进一步的化学转化中探索合成化合物的实用性.
主要方法:
- 从高价前体和三甲酸盐盐中在现场生成乙烯基乙烯基二醇 (乙烯基EBX).
- 乙-EBX与硫醇的反应,产生二乙.
主要成果:
- 在40-97%的产量中成功合成了基二甲酸.
- 证明了产品进一步改造为功能化的 ketene dithioacetals.
- 报告了从产品中合成各种S替代异环.
结论:
- 开发的方法提供了一个容易和高收益的途径,以 ketene dithioacetals.
- 合成的化合物作为有价值的中间体,用于构建复杂的有机分子和异环.
相关概念视频
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
3.4K
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an...
3.4K
α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview
2.9K
The pinacol and McMurry reactions involve the reductive coupling of ketones or aldehydes. Similarly, the bimolecular reductive coupling of two ester molecules in the presence of sodium metal in an aprotic solvent yields an α-hydroxy ketone product. The α-hydroxy ketone is also called acyloin, so the reaction is referred to as ‘acyloin condensation.’
2.9K
Electrophilic Aromatic Substitution: Friedel–Crafts Acylation of Benzene
7.1K
The Friedel–Crafts acylation reactions involve the addition of an acyl group to an aromatic ring. These reactions proceed via electrophilic aromatic substitution by employing an acyl chloride and a Lewis acid catalyst such as aluminum chloride to form aryl ketone.
7.1K
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
α-Alkylation of Ketones via Enolate Ions
3.1K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
3.1K
Acidity of 1-Alkynes
9.9K
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
9.9K


