アルコールとアミンのアミド合成は,二水素の挤出による
Lars Ulrik Nordstrøm1, Henning Vogt, Robert Madsen
1Center for Sustainable and Green Chemistry, Department of Chemistry, Building 201, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.
Journal of the American Chemical Society
|December 9, 2008
まとめ
新しいルテニウム触媒は,アルコールとアミンを結合し,二水素を放出することで,直接のアミド合成を可能にします. このグリーン化学のアプローチは,プライマリ基質から二次アミドを採取する際に,良い収量をもたらします.
科学分野:
- グリーン・ケミストリーと触媒.
- 有機合成による有機合成です.
- オーガノメタリック化学
背景:
- アミド合成は,医薬品や材料において極めて重要です.
- 伝統的な方法は,しばしば厳しい反応剤や複数のステップを伴う.
- 持続可能な触媒経路の開発は,継続的な課題です.
研究 の 目的:
- 直接アミド合成のための環境に優しい方法を提示する.
- アルコール-アミン結合のための単純なルテニウム触媒を使用します.
- この新しいアミド形成の触媒サイクルを探求するために.
主な方法:
- ルテニウム複合体,N-ヘテロサイクリックカルベン,およびフォスフィンから活性ルテニウム触媒のインシット生成.
- プライマリアルコールとプライマリアルキイラミン間の直接結合反応.
- 反応産物および中間物質の特性.
主要な成果:
- プライマリアルコールとプライマリアルキイラミンの二次アミドの合成に成功した.
- 主な副産物として二水素の2つの分子を解放する.
- 中間アルデヒドとルテニウム触媒に調整されたヘミアミナルを含む提案された触媒サイクル.
結論:
- アミド合成のための持続可能で効率的な触媒システムが開発されました.
- この方法は,従来のアミド形成技術よりもグリーンな代替手段を提供します.
- 機械的洞察は,さらなる触媒最適化のための基礎を提供します.
関連する概念動画
Preparation of 1° Amines: Gabriel Synthesis
Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.
Preparation of Amides
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...
Ethers from Alcohols: Alcohol Dehydration and Williamson Ether Synthesis
Overview
Ethers can be prepared from organic compounds by various methods. Some of them are discussed below,
Preparation of Ethers by Alcohol Dehydration
In this method, in the presence of protic acids, alcohol dehydrates to produce alkenes and ethers under different conditions. For example, in the presence of sulphuric acid, dehydration of ethanol at 413 K yields ethoxyethane, whereas it yields ethene at 443 K.
Ethers can be prepared from organic compounds by various methods. Some of them are discussed below,
Preparation of Ethers by Alcohol Dehydration
In this method, in the presence of protic acids, alcohol dehydrates to produce alkenes and ethers under different conditions. For example, in the presence of sulphuric acid, dehydration of ethanol at 413 K yields ethoxyethane, whereas it yields ethene at 443 K.
Aldehydes and Ketones with Amines: Enamine Formation Mechanism
Enamine formation involves the addition of carbonyl compounds to a secondary amine through a series of reactions. The mechanism begins with the generation of carbinolamine, a nucleophilic attack followed by several proton transfer reactions. The hydroxyl group of the carbinolamine is converted into water to make a better leaving group that can push the reaction forward by eliminating a water molecule. In enamine formation, the last step involves the abstraction of a proton from the α carbon to...
Preparation of Amines: Alkylation of Ammonia and Amines
Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines along with a quaternary ammonium salt through successive SN2 reactions. This process of making the quaternary salt through the direct alkylation method is called exhaustive alkylation.
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...


