光によって促進されるアルケンとアミンのコバルト触媒合成
Mason S Faculak1, Alexander M Veatch1, Erik J Alexanian1
1Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA.
まとめ
この研究は,光を用いたアルケンとアミンのアミドを合成するための新しいコバルト触媒法を導入している. この効率的なプロセスは 化学合成に多用途で 原子経済的な経路を提供します
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- アルケンとアミンの直接結合は,貴重な化学化合物の合成に不可欠です.
- アルケンとアミンの直接的な炭素結合のための既存の方法は開発されていないため,効率的なアミド合成が制限されています.
研究 の 目的:
- 直接アルケンの水素アミノカルボニレーションのための一般的,原子経済的な触媒方法を開発する.
- 軽度の反応条件,低圧,およびアミド合成における高い選択性を達成する.
主な方法:
- 軽い,光が促進された条件下で,改変されていないコバルトカルボニルによって触媒化されたアルケンの水素アミノカルボニル化.
- 正式アルケンの水素メチル化のためにシランを用いた連続的なコバルト触媒化アミド還元.
- 溶媒,温度,触媒の負荷を含む反応パラメータの最適化
主要な成果:
- アルケーンとアミン基板の幅広い範囲で高い収量と選択性を実証した.
- 溶媒がない場合でも効率的な触媒作用が得られる.
- フォト解離によって形成されたヒドリドコバルト中間物質を含む触媒機構を提案した.
結論:
- アルケーンとアミンの直接的なアミド合成のための汎用的で効率的な触媒システムを開発した.
- この方法は原子経済的で,穏やかな条件下で動作し,広範囲の基板範囲を提供します.
- この発見は,炭素結合反応の一般的な方法の開発における重要な課題に対応しています.
関連する概念動画
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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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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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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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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.
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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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