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Updated: Jul 22, 2026
13:37
Split-and-pool Synthesis and Characterization of Peptide Tertiary Amide Library
Published on: June 20, 2014
アリル酸アミンの容易かつ選択的製剤のためのフォスフォリミダート再配列
1Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.
Journal of the American Chemical Society
|April 29, 2004
まとめ
アリル酸リン酸化物の新しい[3,3]再配列により,アリル酸リン酸化物が得られます. この方法は,保護されたアルリルアミン,価値ある合成中間物質を効率的に生成します.
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
- リン化学 リン化学
背景:
- アリルアミンは,有機合成における重要な構成要素である.
- アリルアミンの合成のための既存の方法は,範囲や効率が制限される可能性があります.
- リン基の反応剤は,複雑な分子を作るためのユニークな反応性を提供します.
研究 の 目的:
- アリル酸リン酸化物合成のための新しい再配列反応を開発する.
- 容易に入手可能な前駆体から保護されたアリルアミンへの多用途の経路を確立する.
- 新しい再編成方法の範囲と限界を探求する.
主な方法:
- アリルアルコール,アジド,クロロフォスフィートからアリルリン酸化物を作る.
- アリル酸フォスフォリミダートからアリル酸フォスフォリミダートへの熱的[3,3]再配置.
- 保護されたアリル酸アミンを得るために,アリル酸フォスフォラミダートの脱保護と機能化.
主要な成果:
- [3,3]再配列は熱的条件下で進み,アリル酸リン酸化物の単一同位体を生成する.
- この反応は,出発材料の様々な置換パターンに対する耐性を示しています.
- その後,エタネチオラートと酸で治療すると,保護されたアリルアミンを成功裏に生成します.
結論:
- アリル酸フォスフォリミダートの新しく効率的な[3,3]再配列が発見されました.
- この方法論は,鍵となるアリルアミン中間体へのアクセスのための多用途な戦略を提供します.
- 開発された手順は,合成化学者にとって魅力的な経路を提供します.
関連する概念動画
01:07Acid Halides to Amides: Aminolysis
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...
01:07Preparation of Acid Anhydrides
One of the methods for preparing symmetrical or unsymmetrical acid anhydrides involves the treatment of acid chlorides with the sodium salt of carboxylic acids. The reaction proceeds via a nucleophilic acyl substitution.
The carboxylate ion acts as a nucleophile that attacks the carbonyl carbon of the acid chloride to form a tetrahedral intermediate. Subsequently, the re-formation of the carbonyl group with the loss of the chloride ion as a leaving group leads to the formation of an acid...
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01:38Preparation of Amines: Reductive Amination of Aldehydes and Ketones
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01:07Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.
01:28Preparation of 1° Amines: Gabriel Synthesis
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Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
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01:26Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...