通过C-O脱氧而非C-N去胺的胺键的异性基性二功能化
Feng Liu1,2, Xueyuan Yan3, Fangfang Cai1
1Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China.
Nature communications
|February 3, 2025
概括
这项研究引入了一种新的胺基的基化功能失调,使选择性C-O或C-N键裂变成为可能. 这种多功能有机合成方法有效地从胺基中产生propargyl amines和酒精.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 胺转化在有机合成和药物发现中至关重要.
- 现有的胺功能化的方法是有限的.
研究的目的:
- 开发一种新的,不同的基化二功能化胺.
- 为了在单次转换中实现选择性的C-O或C-N键裂解.
主要方法:
- 胺与有机金属核的反应,形成四面体中间体.
- 基于N替代或乙烯基组修改的选择性C-O或C-N裂变.
- 在现场生成和捕获的alkynyl核友.
- 密度函数理论 (DFT) 计算以阐明选择性.
主要成果:
- 实现了氨基酸胺的分离基基性功能失调.
- 已证明有选择性的C-O裂变产生了propargyl酒精.
- 已证明有选择性的C-N裂变产生了propargyl amines.
- 建立了广泛的基质范围,包括生物活性分子的后期修改.
结论:
- 开发的反应提供了一种新的胺转化方式,超越了传统的核酸添加.
- 这种方法可以有效地获取有价值的甲基胺和甲基醇产品.
- 突出了反应在有机合成和药物发现中的广泛适用性.
相关概念视频
Aldol Condensation with β-Diesters: Knoevenagel Condensation
2.9K
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.
2.9K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
5.6K
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
5.6K
Amines to Alkenes: Cope Elimination
2.0K
Cope elimination reaction involves the conversion of tertiary amines to alkene using hydrogen peroxide under thermal conditions, as depicted in figure 1.
2.0K
Amines to Amides: Acylation of Amines
2.4K
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
2.4K
Amides to Carboxylic Acids: Hydrolysis
3.1K
Amides can undergo either acid-catalyzed hydrolysis or base-promoted hydrolysis through a typical nucleophilic acyl substitution. Each hydrolysis requires severe conditions.
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
3.1K
Preparation of Amides
3.0K
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
3.0K


