异化物作为MHAT与未激活基反应中的受体组
Jordi Puig1, Josep Bonjoch1, Ben Bradshaw1
1Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, Av. Joan XXIII 27-31, 08028 Barcelona, Spain.
Organic letters
|August 30, 2023
概括
这项研究引入了对金属化物原子转移 (MHAT) 合反应的异化物,使得从烯中有效合成各种异环. 该方法为简单的基提供了直接循环,对于更复杂的基,提供了两步过程.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 异环化学 异环化学
背景情况:
- 金属化物原子转移 (MHAT) 反应对C-C键的形成有价值.
- 异化物是有机合成中的多功能构建块.
- 替代异环的高效合成仍然是一个关键的挑战.
研究的目的:
- 开发一种使用异酸盐合成异环的新方法.
- 探索MHAT与异化物和非活化基的合反应的应用.
- 为了证明开发的方法对各种异环基架的广泛实用性.
主要方法:
- 在MHAT合反应中利用异化物作为受体组.
- 用于单替代基的直接合和循环.
- 开发了一种两步,一的程序 (MHAT减小循环,然后是MHATMinisci合),用于更多的替代.
主要成果:
- 成功合和循环循环的单替代基直接.
- 实现了多种替代异环的合成,包括氨酸,醇和异类素.
- 证明了MHAT合和Minisci合序列对复杂基板的多功能性.
结论:
- 描述的方法提供了一个有效的途径,以替代异环.
- 异化物在MHAT合反应中作为有效的受体组,用于异环合成.
- 开发的两步程序扩大了复杂基底的MHAT反应的范围.
相关概念视频
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.3K
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.
18.3K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
2.8K
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
2.8K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
3.8K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
3.8K
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
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
8.6K
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.
8.6K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
3.2K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
3.2K


