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Updated: Feb 1, 2026
08:40
Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules
Published on: April 28, 2014
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単純アルケニルアミドのニッケル触媒化1,2-ディアリレーション
Joseph Derosa1, Roman Kleinmans1, Van T Tran1
1Department of Chemistry , The Scripps Research Institute , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
Journal of the American Chemical Society
|December 12, 2018
まとめ
この研究は,単純なアミドとアリル化合物から1,2-ダイアリル化製品を作るための新しいニッケル触媒反応を導入する. この方法は,有機合成における優れた地域制御のために,電子欠乏のオレフィンリガンドを使用する.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- 交互結合反応は有機合成に不可欠です
- 複雑な分子合成のための地域選択的方法の開発は,依然として課題です.
- アミド機能群は,触媒作用における誘導群に挑戦することがあります.
研究 の 目的:
- ニッケル触媒による 結合結合反応を報告する
- アルケニルアミドの地域制御された1,2-ディアリレーションを実現する.
- 電子欠乏性オレフィンリガンドの交互結合における有用性を調査する.
主な方法:
- ニッケル触媒によるクロスカップリング反応
- 単純なアルケニルアミド,アリルイオジド,アリルボロンエステルを使用した.
- 電子欠乏オレフィン (EDO) リガンドとして使用されている.
- 収穫量と地域選択性の最適化反応条件
主要な成果:
- 優れた地域制御で1,2-ディアリレート製品を 合成した.
- 3-ブテノ酸,4-ペンテノ酸,およびアリルアミンから派生した幅広いアミドとの互換性が実証されています.
- これは,本来のアミド群によって導かれた,地域制御の1,2ダイアリレーションが報告された最初の例である.
- 計算分析により,反応機構とリガンドの役割に関する洞察が得られた.
結論:
- 地域制御の1,2ダイアリレーションの 新しく効率的な方法を開発した.
- EDOリガンドの使用は反応の成功に不可欠です.
- この方法論は,アミド誘導クロスカップリング反応の範囲を拡大する.
関連する概念動画
01:29Preparation of Amides
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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...
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01:28Amides to Carboxylic Acids: Hydrolysis
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Amides can undergo either acid-catalyzed hydrolysis or base-promoted hydrolysis through a typical nucleophilic acyl substitution. Each hydrolysis requires severe conditions.
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
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01:19Amines to Amides: Acylation of Amines
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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...
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01:07Acid Halides to Amides: Aminolysis
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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...
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02:24Acid-Catalyzed Ring-Opening of Epoxides
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Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
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02:26Base-Catalyzed Ring-Opening of Epoxides
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Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
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