アミドの銅触媒によるN-アリレーションに関するメカニズム研究
Eric R Strieter1, Brijesh Bhayana, Stephen L Buchwald
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|December 17, 2008
まとめ
この研究は,アミドのN-アリレーションのための銅触媒化されたゴールドバーグ反応を詳細に説明しています. 発見は,活性銅種とアリルハリドの活性化メカニズムを制御するダイアミンリガンドの役割を強調しています.
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
- 反応メカニズム 反応メカニズム
背景:
- ゴールドバーグ反応は,アミドの銅触媒によるN-アリレーションであり,合成化学において貴重な化合物を生成するために不可欠です.
- この反応のメカニズムを理解することは,産業や学術研究におけるその応用を最適化するために極めて重要です.
研究 の 目的:
- アミドの触媒的およびステキオメトリックのN-アリレーションの両方のメカニズム的詳細を解明する.
- 銅触媒反応におけるケラティングダイアミンリガンドの役割を調査する.
- アリルハリドの活性化に関する洞察を提供するため.
主な方法:
- 銅触媒によるN-arylationのメカニズム的調査.
- 前製銅 (((I) アミダート複合体を用いたステキオメトリック反応の研究.
- アリルヨウ酸化物のN-アリレーションに関する運動学的研究.
主要な成果:
- シェレティングダイアミンリガンドは,活性触媒種の濃度を制御するために重要である.
- アリルハリドの活性化のための1,2-ダイアミン結合銅(I) アミダート複合体を含む一貫したメカニズムが提案されました.
- 動力学的データは,アリルハリド活性化のための提案されたメカニズムを支持します.
結論:
- この研究は,ゴールドバーグ反応の詳細なメカニズム的理解を提供します.
- この発見は,銅触媒によるN-arylationにおけるリガンド設計の重要性を強調しています.
- この研究は,N-アリレートアミドの効率的な合成に貢献しています.
関連する概念動画
Preparation of Amines: Reduction of Amides and Nitriles
Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an amino group with an extra carbon in the skeleton. Nitriles are formed from the reaction between alkyl halides and sodium cyanide through the SN2 mechanism. Primary alkyl halides are the preferred substrates to prepare nitriles.
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...
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 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...
Amides to Carboxylic Acids: Hydrolysis
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...
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.


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