通过sp3的Azepinoindoles的多样性导向合成C-H功能化和骨重塑
Yao-Bin Shen1, Fen Ma2, Hao-Qi Song2
1College of Chemistry, Chemical Engineering and Materials Science, Zaozhuang University, Zaozhuang, Shandong 277160, P. R. China.
Organic letters
|December 11, 2025
概括
这项研究引入了一种新的分子编辑方法,可以通过环扩张合成复杂的阿齐皮诺因多尔. 无金属方法为晚期药物修饰提供了多功能性.
科学领域:
- 有机化学 有机化学
- 药用化学 医学化学
- 合成化学 合成化学
背景情况:
- 晚期分子编辑N-异环增强了化合物的复杂性和多样性.
- 为了合成阿齐皮诺因多尔,同时对皮罗利丁的外周和骨进行编辑是具有挑战性和未被充分探索的.
研究的目的:
- 开发一种新的方法,用于Azepinoindoles的分离合成.
- 通过骨重塑和C-H功能化,使罗利丁的后期分子编辑成为可能.
主要方法:
- 以乙醇为媒介的氧化还原sp3 C-H 功能化,利用 tert-amino 效应.
- 三酸促进的骨重塑,包括罗利丁环扩张.
主要成果:
- 实现了阿泽皮诺[4,3,2-cd]醇和阿泽皮诺[2,3-e]醇的分离合成.
- 证明了无金属反应条件,具有出色的功能组兼容性.
- 展示了可扩展性,操作简单性和药物分子晚期修改的潜力.
结论:
- 开发的方法显著扩大了pyrrolidine分子编辑的范围.
- 这种方法为复杂的异环化合物的以多样性为导向的合成提供了一个多功能平台.
- 机理学研究验证了拟议的反应途径.
相关概念视频
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
3.3K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
3.3K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
12.1K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
12.1K
Preparation of 1° Amines: Azide Synthesis
4.5K
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
4.5K
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
3.6K
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para...
3.6K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
5.3K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
5.3K
Diels–Alder Reaction: Characteristics of Dienes
5.0K
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable,...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable,...
5.0K


