不对称的Dearomative双重功能通过重新调味阻断的硫 Claisen重排
Sheng Ye1, Yanping Liu1, Guoqing Liang1
1Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, China.
Angewandte Chemie (International ed. in English)
|March 9, 2026
概括
这项研究抑制了芳香的克莱森重新排列的重新芳香化,以实现不对称的芳香双重功能. 在低温下重新排列的基拉尔硫胺允许拦截不稳定的中间体,产生复杂的基拉尔产品.
科学领域:
- 有机化学 有机化学
- 不对称的合成方法
- 反应机制的反应机制
背景情况:
- 芳香的克莱森重新排列通常会产生不稳定的淡味中间体,这些中间体会迅速重新调味.
- 拦截这些短暂的中间体对于开发新型合成途径至关重要.
- 现有的方法缺乏有效的策略来抑制再芳香化并实现不对称的功能化.
研究的目的:
- 开发一种方法来抑制芳香的克莱森重组中的淡香中间体的重新芳香化.
- 为了使芳香化合物的不对称的芳香双重功能化.
- 为了合成具有多个立体中心的复杂性分子.
主要方法:
- 开发了一种非对称的脱水重排合利硫化物.
- 在极低温度 (-95°C) 进行反应以稳定反应中间体.
- 采用各种核 (烯乙烯,有机试剂,异原子核) 进行中间捕获.
主要成果:
- 成功抑制了昂贵的芳香中间体的不可避免的重新芳香化.
- 实现了不对称的芳香双重功能,产生了多达四个连续立体中心的产品.
- 演示了三种不同的脱硫路径,导致具有轴向和点向性的结构多样化的性产品.
结论:
- 开发的方法提供了一种独特的策略,用于控制 dearomatized中间体的反应性.
- 通过一种新的 Dearomatization 多路径,使复杂的性分子的合成成为可能.
- 计算研究阐明了机制,并证实了性转移的高保真性.
相关概念视频
![[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F13097.jpg&w=3840&q=75)
01:24[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
2.9K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
2.9K
02:23SN2 Reaction: Stereochemistry
12.3K
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
12.3K
01:08Esters to β-Ketoesters: Claisen Condensation Mechanism
4.9K
Regular Claisen condensation involves the synthesis of β-ketoesters by combining identical ester molecules bearing two α hydrogens in the presence of an alkoxide base. The reaction commences with the deprotonation of the acidic α hydrogen by the base to form a resonance stabilized ester enolate. This nucleophilic ion then attacks the carbonyl center of another ester molecule to generate a tetrahedral alkoxide intermediate. Next, the expulsion of the alkoxide group from the...
4.9K
01:18β-Dicarbonyl Compounds via Crossed Claisen Condensations
3.9K
Crossed Claisen condensations are base-promoted reactions between two different ester molecules producing β-dicarbonyl compounds. The reaction involving esters, with both containing α hydrogen, results in a mixture of four different products that are difficult to isolate. This reduces the synthetic utility of the reaction.
3.9K
02:26Preparation and Reactions of Sulfides
5.9K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
5.9K
01:33Aldol Condensation vs Claisen Condensation
8.2K
Aldol condensation is an acid or base-catalyzed condensation between aldehydes or ketones to give an α,ꞵ-unsaturated carbonyl compound. A base-promoted condensation between ester molecules to produce a ꞵ-ketoester is known as the Claisen condensation. In the presence of a base, both reactions involve deprotonation of the acidic α hydrogen to produce the corresponding enolates. The nucleophilic enolates attack their respective nonenolized carbonyl compound forming a tetrahedral...
8.2K