作为高效的一氧化碳释放分子的碳酸:在催化碳化反应中的合成和应用
Stig D Friis1, Rolf H Taaning, Anders T Lindhardt
1Center for Insoluble Protein Structures (inSPIN), Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|October 22, 2011
概括
碳酸提供了一种稳定而高效的方法,用于化学反应产生一氧化碳. 这项研究表明,它们在催化合和标记生物活性化合物的成功使用.
科学领域:
- 有机化学 有机化学
- 合成有机化学 合成有机化学
- 催化剂是一种催化剂.
背景情况:
- 一氧化碳 (CO) 是有机合成中关键的C1构建块.
- 传统的二氧化碳来源带来了处理和安全方面的挑战.
- 碳酸为产生二氧化碳提供了一个新的,稳定的替代方案.
研究的目的:
- 为了合成和表征新型碳酸.
- 评估它们作为一氧化碳前体的效率.
- 为了证明它们在催化碳基联结和生物标签中的应用.
主要方法:
- 从基和二氧化碳中合成碳酸.
- 使用各种激活剂进行脱碳化研究.
- 帕拉催化碳酸合反应.
- 合成和应用同位素标记的碳酸 (MePh(2) Si(13) CO(2) H).
主要成果:
- 碳酸是空气稳定的,易于处理.
- 从晶体MePh(2) SiCO(2) H中实现了高效的CO释放.
- 在催化碳聚合物合物中成功应用,具有近静态度的CO前体.
- 在生物活性分子的碳基标记中证明了实用性.
结论:
- 碳酸是一氧化碳的有效和方便的前体.
- 它们在碳酸合物和生物标记中的应用提供了实际的合成优势.
- 这项工作扩大了利用CO在有机合成中的工具包.
相关概念视频
Loss of Carboxy Group as CO2: Decarboxylation of Malonic Acid Derivatives
Just like β-keto acids—which upon thermal decarboxylation form ketones—β-dicarboxylic acids undergo decarboxylation to generate monocarboxylic acids with the liberation of carbon dioxide.
Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents
Carboxylic acids can be prepared by the carboxylation of Grignard reagents (RMgX). This method is convenient for converting alkyl (primary, secondary or tertiary), vinyl, benzyl, and aryl halides to carboxylic acids with one additional carbon than the starting RMgX.
Reactions of Carboxylic Acids: Introduction
Carboxylic acids possess an acidic –COOH functional group. The acidity can be attributed to the resonance stabilization of their conjugate base, wherein the negative charge is delocalized over both oxygen atoms.
Loss of Carboxy Group as CO2: Decarboxylation of β-Ketoacids
Carboxylic acids, upon heating, undergo a decarboxylation reaction by releasing carbon dioxide gas. Monocarboxylic acids do not undergo decarboxylation easily. However, a silver salt of carboxylic acid reacts with bromine or iodine under high temperature to release carbon dioxide gas and forms halide with one less carbon. This reaction is called the Hunsdiecker reaction.
Preparation 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.
Preparation of Carboxylic Acids: Overview
There are various methods for the preparation of carboxylic acids. For example, oxidation of primary alcohols or aldehydes using strong oxidizing agents results in a carboxylic acid. Aldehydes can also be oxidized in the presence of mild oxidizing agents.


