アリルフッ化物のアミネーションを誘導する
Qi-Kai Kang1,2, Yunzhi Lin1,2, Yuntong Li1,2
1Institute of Natural Sciences , Westlake Institute for Advanced Study , 18 Shilongshan Road , Hangzhou 310024 , Zhejiang , China.
Journal of the American Chemical Society
|February 11, 2020
まとめ
この研究は,アリルフッ素を用いた新しいルテニウム触媒核性芳香置換 (SNAr) 反応を導入している. 開発されたヘミラビルリガンドは,電子豊富な中性アレーンの効率的なアミネーションを容易にし,合成経路を簡素化します.
科学分野:
- 有機金属化学
- カタリシス
- 有機合成
背景:
- 核性アロマティック置換 (SNAr) 反応は有機合成において基本的なものです.
- アリルフッ素は,強い炭素-フッ素結合により,しばしばSNArに対する挑戦的な基質である.
- アリルフッ素のSNArのための効率的な触媒システムの開発は,活発な研究分野です.
研究 の 目的:
- アリルフッ化物に対する新しいルテニウム (Ru) 催化SNAr反応を開発する.
- 触媒活性強化におけるヘミラビルリガンドの役割を調査する.
- 余分な基板を必要とせずに,電子豊富な中性アレーンのアミネーションを可能にします.
主な方法:
- ルテニウム触媒反応の発展
- ヘミラビルリガンドを用いて触媒の性質を修正する.
- アリルフッ素を制限剤として使用する.
- η6複合体の形成に関するメカニズム研究.
主要な成果:
- アリルフッ素のSNアミナ化は,Ru/hemilabile-ligand触媒を用いて成功しました.
- 有意なリガンド強化が観察され,電子豊富なアレンと中性アレンの両方の反応を可能にしました.
- 反応は過剰なアレン基板を必要とせずに効率的に進行した.
- メカニズム研究により,ルアレン η6複合体の形成と,ヘミラビルリガンドによって促進された産物解離が示された.
結論:
- アリルフッ化物のSNArのための新しい効率的なRu/hemilabile-ligand触媒システムが開発されました.
- ヘミラビルリガンドは,製品放出を促進することによって,触媒サイクルを促進する上で重要な役割を果たします.
- この方法論は,アリルフッ素からアミナ化アレンを合成するための簡素化されたアプローチを提供します.
関連する概念動画
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
7.3K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
7.3K
Nucleophilic Aromatic Substitution: Elimination–Addition
4.9K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.9K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
2.3K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
2.3K
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
2.6K
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
2.6K
Amines to Alkenes: Hofmann Elimination
3.1K
Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. This is accomplished by treating the amine with an excess of alkyl halide, which results in a halide salt. Next, the halide salt is transformed into a hydroxide salt that functions as a base to enable elimination.
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
3.1K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
3.6K
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.
3.6K

![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
