関連する実験動画
Updated: Jun 9, 2026
08:43
Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
二次アミドの制御および化学選択的還元
Guillaume Pelletier1, William S Bechara, André B Charette
1Department of Chemistry, Université de Montréal, P.O. Box 6128, Station Downtown, Montréal, Québec, Canada H3C 3J7.
Journal of the American Chemical Society
|August 26, 2010
まとめ
本研究では,二次アミドをイミン,アルデヒド,アミンに還元するための金属のない方法が紹介されています. 効率的なプロセスは,穏やかな条件下で動作し,さまざまな機能群を許容します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成方法論 合成方法論
背景:
- 二次アミドは,有機合成における多機能機能群である.
- アミド還元のための効率的で選択的な方法は,多様な分子構造へのアクセスに不可欠です.
研究 の 目的:
- 二次性アミドのための新しい金属フリー還元戦略を開発する.
- 二次性アミドをイミン,アルデヒド,アミンに化学選択的に変換できるようにする.
主な方法:
- トリフリックアンヒドリドと2-フッ素ピリジンを使用して二次アミドの活性化.
- トライエチルシランで活性化アミドをイミニウム種に還元する.
- イミンの分離,または加工によってアルデヒドへの変換.
- アミンをアクセスするためのワンポット還元性アミネーション.
主要な成果:
- 二次性アミドからイミン,アルデヒド,アミンの良好から優れた収量を達成した.
- 高い化学選択性と,様々な機能群に対する耐性を示した.
- この方法論は,簡単に入手可能な試薬を用いて,環境の温度と圧力下で動作します.
結論:
- 開発された金属のない方法は,二次アミド変換のための効率的で汎用的な経路を提供します.
- このアプローチは,軽度で選択的な条件下でイミン,アルデヒド,アミンへのアクセスを提供します.
- この戦略は,有機化学で複雑な分子を合成するのに価値があります.
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関連する概念動画
01:13Preparation of Amines: Reduction of Amides and Nitriles
Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an amino group with an extra carbon in the skeleton. Nitriles are formed from the reaction between alkyl halides and sodium cyanide through the SN2 mechanism. Primary alkyl halides are the preferred substrates to prepare nitriles.
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...
01:38Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.
01:20Amides to Amines: LiAlH4 Reduction
Amide reduction with strong reducing agents like lithium aluminum hydride proceeds through a nucleophilic acyl substitution to form amines. Primary, secondary, and tertiary amides yield primary, secondary, and tertiary amines, respectively.
Amide reduction requires two equivalents of the reducing agent, acting as a source of hydride ions. As shown in the figure, the reaction is initiated with a nucleophilic attack by the hydride ion at the carbonyl carbon to form a tetrahedral intermediate.
Amide reduction requires two equivalents of the reducing agent, acting as a source of hydride ions. As shown in the figure, the reaction is initiated with a nucleophilic attack by the hydride ion at the carbonyl carbon to form a tetrahedral intermediate.
01:29Preparation of Amines: Reduction of Oximes and Nitro Compounds
Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
01:22Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
00:55Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...