Pd触媒によるアルキイラミンによる分子間C-Hアミネーション
Eun Jeong Yoo1, Sandy Ma, Tian-Sheng Mei
1Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Journal of the American Chemical Society
|April 28, 2011
まとめ
この研究は,アリアルキルアミンを合成するための新しい触媒方法を示しています. これは,C-Hアミネーションのためのパラジウム触媒を使用し,ベンゾ酸から貴重なアミン製品への直接的な経路を提供します.
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:
- C-Hアミネーションは,有機合成における重要な変換である.
- アミン合成のための効率的な触媒システムの開発は,依然として活発な研究分野です.
- C-Hボンドの直接機能化は,原子経済的な合成経路を提供します.
研究 の 目的:
- N-アリルベンザミドの新しい触媒C-Hアミネーションを開発する.
- O-ベンゾイルヒドロキシラミンをアミネート剤として使用することを調査する.
- 二次および三次アリアルキルアミンを合成するためのワンポット手順を確立する.
主な方法:
- パラジウム (II) とパラジウム (0) は,C-Hアミナーション反応を触媒化した.
- O-ベンゾイルヒドロキシラミンを主要反応剤として利用する.
- 二次アミンとベンゾイル過酸化物からO-ベンゾイルヒドロキシラミンの局所生成を含むワンポット手順.
主要な成果:
- N-アリルベンザミドのC-Hアミネーションは,Pd触媒を用いて成功しました.
- 二次アミンとベンゾイル過酸化物を用いたワンポット法が開発されました.
- この反応により,三次性アリアルキルアミンの合成と二次性アリアルキルアミンの合成が収束します.
結論:
- アリアルキルアミンの合成のための新しい触媒分離が確立されました.
- 開発された方法論は,ベンゾ酸から有価なアミン製品への汎用的な経路を提供します.
- この研究は,複雑なアミン構造を構築するためのツールキットを拡張します.
関連する概念動画
01:28Preparation of 1° Amines: Gabriel Synthesis
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...
01:30Preparation of Amines: Alkylation of Ammonia and Amines
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...
01:38Preparation of Amines: Reductive Amination of Aldehydes and Ketones
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.
02:27Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
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...
02:24Reduction 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.