非活性化オレフィンをダイアキラミンで水素アミノアルキル化
Seth B Herzon1, John F Hartwig
1Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
Journal of the American Chemical Society
|October 22, 2008
まとめ
この研究は,活性化されていないアミンとオレフィンを結合するための新しいタンタール触媒反応を導入しています. このプロセスは,基板の前活性化なしに,枝分かれした製品を効率的に形成し,希少な分子間アミン-オレフィン結合を示します.
科学分野:
- 有機金属化学 有機金属化学
- カタリシス カタリシス カタリシス
- オーガニック・シンセシス オーガニック・シンセシス
背景:
- 分子間アミン-オレフィン結合反応には,しばしば基質の前活性化が必要です.
- 直接的なC-H機能化のための触媒システムの開発は,有機合成の主要な課題です.
研究 の 目的:
- 活性化されていないオレフィンに活性化されていないダイアキラミンを分子間添加するための新しい触媒的方法について説明する.
- この新しいアミン-オレフィン結合反応の範囲とメカニズムを調査する.
主な方法:
- クロロアミドタンタール複合体, [TaCl3(NEt2) 2) 2 (2) を触媒として使用した.
- 反応機構を明らかにするために,1H NMRスペクトロスコーピーとデウテリウムラベリング実験を行いました.
- 関連するクロロアニリド複合体[TaCl3(NMePh) ]2 (4) の触媒活性を調べました.
主要な成果:
- 高い収穫率 (96%まで) と,枝分かれした挿入製品の選択性を達成しました.
- メチラミンの一次C-H結合と,より高いダイアキラミンの一次C-H結合をカップリングする反応の能力を実証した.
- 複合体4を用いてオレフィンにN-アルキル-アリラミンを90°Cで触媒的に添加することを実証した.
結論:
- この反応は,ターンオーバーを制限するエタ2イミン複合体の生成を経由して進行する.
- 触媒の構造と基板の分割は反応性に影響し,混合ハライドアミド触媒はより高い活性を示しています.
- この研究は,基板の前活性化なしで分子間アミン-オレフィン結合のための希少で効率的な方法を提供します.
さらに関連する動画
関連する概念動画
Amines to Amides: Acylation of Amines
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 amide...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
Preparation 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...
Preparation 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...
Acid 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...
Preparation 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...
Aldehydes and Ketones with Amines: Enamine Formation Mechanism
Enamine formation involves the addition of carbonyl compounds to a secondary amine through a series of reactions. The mechanism begins with the generation of carbinolamine, a nucleophilic attack followed by several proton transfer reactions. The hydroxyl group of the carbinolamine is converted into water to make a better leaving group that can push the reaction forward by eliminating a water molecule. In enamine formation, the last step involves the abstraction of a proton from the α carbon to...


