在水溶液中,用白银催化解碳氧化碳酸的异性碳氧化化
Feng Yin1, Zhentao Wang, Zhaodong Li
1Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
Journal of the American Chemical Society
|June 15, 2012
概括
这项研究引入了一种用于制造化化合物的新方法. 它使用酸银来催化碳酸化,在温和条件下有效地产生基化物.
科学领域:
- 有机化学 有机化学
- 化学 的化学
背景情况:
- 化化合物在各种工业中至关重要.
- 形成碳-键,特别是在特定地点,仍然很困难.
研究的目的:
- 开发一种高效实用的合成化的方法.
- 探索一种新的催化方法来形成C(sp(3)) -F键.
主要方法:
- 使用酸银 (AgNO(3)) 作为催化剂.
- 使用SELECTFLUOR®作为化试剂.
- 在温和条件下在水溶液中进行反应.
主要成果:
- 实现了各种异性碳酸酸的高效脱碳化化.
- 在令人满意的产量中合成了相应的基化物.
- 证明了该方法的通用性,化学选择性和功能组兼容性.
结论:
- 开发的激光化方法对于合成化分子非常实用.
- 一个拟议的机制涉及Ag(III) 介导的单电子转移和原子转移.
- 这种催化脱碳氧化为有机合成提供了一种有价值的工具.
相关概念视频
01:01Acid Halides to Carboxylic Acids: Hydrolysis
Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
01:14α-Halogenation of Carboxylic Acid Derivatives: Overview
Unlike aldehydes and ketones, carboxylic acids do not readily participate in α halogenation reactions via enols or enolate intermediates. However, α-halogenated acids are obtained through other methods. One of the approaches is the Hell–Volhard–Zelinsky (HVZ) reaction, wherein the carboxylic acid is treated with halogen in the presence of PBr3. It involves the conversion of acid to acid halide, which exists in equilibrium with its enol form. The enol attacks the electrophilic halogen to produce...
01:13Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism
Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.
01:21Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
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...
01:19Preparation of Carboxylic Acids: Hydrolysis of Nitriles
Nitriles (R–CN) can be converted into carboxylic acids (R–COOH) upon treatment with aqueous acids, i.e., upon hydrolysis of nitriles. Under base-catalyzed conditions, carboxylate anions (R–COO−) are formed.
01:17Carboxylic Acids to Primary Alcohols: Hydride Reduction
Carboxylic acids, upon reaction with strong reducing agents such as lithium aluminum hydride followed by hydrolysis, undergo reduction to form primary alcohols.