アミノキノリン誘導型,銅触媒型 sp ((2) C-H結合アミネーションの一般的な方法
1Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
Journal of the American Chemical Society
|March 19, 2016
まとめ
新しい銅触媒反応により,空気を酸化剤として使用してベンゾ酸誘導体のアミナ化が可能になる. この方法は,様々なプライマリ・アミンとセカンダリ・アミンを効果的に結合することで,幅広い範囲を示しています.
科学分野:
- 有機化学
- キャタリシス
- 合成方法論
背景:
- C-H結合の機能化は有機合成の重要な領域である.
- C-N結合形成の効率的な方法の開発は,薬剤発見と材料科学にとって不可欠です.
- 銅の触媒は有機変異に費用対効果の高い多角的なアプローチを提供します.
研究 の 目的:
- ベンゾ酸誘導体におけるβ-C ((sp ((2)) -H結合のアミナ化のための一般的で操作的に単純な方法を開発する.
- 銅の触媒とアミノキノリンの誘導基を効率的なC-Hアミネーションのために利用する.
- 開発された方法論の範囲と限界を,多様なアミン結合パートナーと探求する.
主な方法:
- 銅 (II) アセテートまたは基本銅 (II) 炭酸を触媒として使用した銅触媒反応.
- アミノキノリンリガンドを用いて,ベンゾ酸誘導体のβ位置にアミネーションを誘導する.
- 大気中の酸素を最終酸化剤として利用する.
- アリファティック,アロマティック,ヘテロサイクリック,およびスルフォナミド誘導体を含む様々な一次および二次アミンのスクリーニング.
主要な成果:
- ベンゾ酸誘導体のβ-C(sp(2)) -H結合の成功アミネーションが達成された.
- この反応は,高い操作のシンプルさと一般性を示した.
- 主要・次要のアリファティック・アロマティック・アミン,インドール,ピラゾール,カルバゾール,スルフォナミドなど,幅広いアミンカップリングパートナーが有能であった.
- 電子欠乏性アロマティック・アミンとヘテロアロマティック・アミンは,結合に効果的に参加した.
結論:
- 報告された方法は,銅で触媒化されたC-Hアミネーションのための効率的で汎用的な経路を提供します.
- 反応の広範囲の基板,特に多様なアミン結合パートナーは,その実用的な有用性を強調します.
- この方法論は,複雑な有機分子におけるC−N結合の構築に役立つツールである.
関連する概念動画
Preparation of 1° Amines: Azide Synthesis
4.8K
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...
4.8K
Preparation of Amines: Alkylation of Ammonia and Amines
5.0K
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...
5.0K
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
4.2K
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.
4.2K
Amines to Amides: Acylation of Amines
3.7K
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...
3.7K
Acid Halides to Amides: Aminolysis
4.6K
Aminolysis is a nucleophilic acyl substitution reaction, where ammonia or amines act as nucleophiles to give the substitution product. Acid halides react with ammonia, primary amines, and secondary amines to yield primary, secondary, and tertiary amides, respectively.
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
4.6K
Preparation of 1° Amines: Gabriel Synthesis
4.9K
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...
4.9K


![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)