イリジウム触媒による非活性化アリファ酸アルケンの分子間水素アミネーションで,アミドやスルフォナミドが用いられる
Christo S Sevov1, Jianrong Zhou, John F Hartwig
1Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
Journal of the American Chemical Society
|July 12, 2012
まとめ
この研究は,活性化されていないアルケーンにN-H結合を加えることで,N-アルキイラミンを合成するための新しい触媒的方法を提示しています. 効率的な反応により,アリラミドとスルフォナミドから保護されたアミン産物が得られます.
科学分野:
- 有機化学 オーガニック・ケミストリー
- カタリシス カタリシス カタリシス
- 合成方法論 合成方法論
背景:
- 活性化されていないアルケーンにN-H結合を分子間添加することは,難しいが望ましい合成戦略です.
- N-アルキイラミンは,有機合成における貴重な構成要素である.
研究 の 目的:
- 活性化されていないアルケンの分子間アミネーションのための触媒的方法の開発.
- アリラミドとスルフォナミドを用いて保護されたアミン産物を合成する.
主な方法:
- 触媒的分子間アミネーション反応.
- サブストラットとして未活性化されたα-オレフィンとビサイクロアルケンを利用した.
- N-Hボンドドナーとしてアリラミドとスルフォナミドを使用した.
主要な成果:
- 合成的に有用な保護アミン製品の高収量を達成しました.
- 活性化されていないα-オレフィンとバイサイクロアルケンの分子間アミナ化を実証した.
- N-H結合の酸化添加とアミドの調整を含む触媒的静止状態を特定しました.
結論:
- アルケンのN-アルキル化のための新しい効率的な方法を開発しました.
- アミド解離と分子内再編成を含む主要なメカニズム的ステップを明らかにした.
- 保護されたN-アルキイラミンへの貴重な経路を提供します.
関連する概念動画
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
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...
01:22Preparation 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...
02:40Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Introduction
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
01:29Preparation of Amides
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...