鉄で触媒化された多元カスケード・クロスカップリングの一般的方法
Lei Liu1, Maria Camila Aguilera2, Wes Lee1
1Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA.
Science (New York, N.Y.)
|October 21, 2021
まとめ
鉄の触媒は新しい多成分クロスカップリング反応を可能にします この研究は,循環性フッ素化合物を合成するための鉄触媒式無効クロスカップリングプロトコルを導入し,このような反応における鉄の以前の制限を克服しました.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- 化学合成において,過渡金属触媒によるクロスカップリング反応は不可欠である.
- 鉄 (Fe) は,触媒としての利点 (コスト,豊富さ,低毒性) を提供しているが,多成分クロスカップリングでの使用は限られている.
- これまでの方法では,複雑な多元結合に鉄をうまく利用できませんでした.
研究 の 目的:
- 多成分クロスカップリング反応のための新しい鉄触媒方法を開発する.
- 鉄触媒を用いた循環性フッ素化合物の合成を可能にします.
- 鉄で触媒化された 激流反応の範囲を広げるため
主な方法:
- Grignardの反応剤によるα-ボリル基の1,2-bis ((dicyclohexylphosphino) エタンの鉄触媒結合の実証.
- 一般的な鉄触媒による多成分無効クロスコップリングプロトコルの開発.
- Fe (II) 種とアルキル基の中間物質を含むメカニズム研究.
主要な成果:
- 鉄触媒によるα-ボリル基とグリナード反応剤の成功結合
- マルチコンポーネントの無効クロスカップリングに関する広く適用可能なプロトコル.
- 多様な循環性フッ素化合物の実用的な合成が達成された.
- Fe (II) とアルキルラジカルを含む触媒サイクルに関する機械的洞察.
結論:
- 鉄の触媒は,複雑な多成分クロスカップリング反応で効果的に使用できます.
- 開発されたプロトコルは,循環性フッ素化合物への実用的な経路を提供します.
- この研究は,有機合成の触媒としての鉄の有用性を拡大し,特に基質媒介による変換に役立ちます.
さらに関連する動画
07:49Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
Published on: February 20, 2020
9.4K
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
11:44Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
25.6K
関連する概念動画
01:11Radical Reactivity: Overview
2.2K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.2K
01:33Radical Reactivity: Intramolecular vs Intermolecular
1.8K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.8K
00:47Radical Formation: Addition
1.9K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
1.9K
01:03Radical Formation: Overview
2.3K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.3K
01:20Radical Reactivity: Concentration Effects
1.6K
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
1.6K
01:16Radical Reactivity: Nucleophilic Radicals
2.2K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.2K