Pd/P ((t-Bu) ((3)):アリル塩化物とアリルブロミドの静止反応のための温和で一般的な触媒
Adam F Littke1, Lothar Schwarz, Gregory C Fu
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|May 30, 2002
まとめ
新しいパラジウム触媒であるPd/P(t-Bu) ((3) は,アリル塩化物とブロミドの静止反応を効率的に可能にします. この突破は,複雑なビアリルと室温結合の合成を可能にし,重要な合成課題を克服しました.
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:
- 静かな反応は,炭素-炭素結合の形成に不可欠である.
- アリル塩化物の結合は,その反応性が低いため,しばしば課題を提示します.
- Stilleカップリングの既存の方法は,基板の範囲と反応条件に制限があります.
研究 の 目的:
- スティール・クロスカップリング反応のための高反応性パラジウム触媒の開発.
- アリル塩化物などの難しい基質の効率的な結合を可能にするために.
- 静かな反応のためのユーザーフレンドリーで一般的な方法を確立する.
主な方法:
- パラジウム触媒複合体,Pd/P(t-Bu) ((3) を利用し,大量のフォスフィンリガンドを特徴としています.
- アリル塩化物とブロミドを含む静止反応における触媒活性の研究.
- オルガノチン反応剤と基板のステリック阻害の範囲を調査する.
主要な成果:
- Pd/P ((t-Bu) ((3) は異常な反応性を示し,幅広い種類のアリル塩化物の静かな結合を可能にします.
- 触媒は,テトラ・オルト・置換化合物を含む,ステリカルに阻害されたビアリルの合成を促進します.
- アリルブロミドの室温静止クロスカップリングのための最初の一般的な方法が達成されました.
結論:
- Pd/P ((t-Bu) ((3)) 触媒システムは,これまで難しかった静止結合に強力な解決策を提供します.
- この方法論は,クロスカップリング反応におけるアリル塩化物とブロミドの合成的有用性を拡大する.
- 触媒の商業的な利用可能性と使いやすさは,有機合成に非常に価値があります.
関連する概念動画
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Dynamic Equilibrium
A reversible chemical reaction represents a chemical process that proceeds in both forward (left to right) and reverse (right to left) directions. When the rates of the forward and reverse reactions are equal, the concentrations of the reactant and product species remain constant over time and the system is at equilibrium. A special double arrow is used to emphasize the reversible nature of the reaction. The relative concentrations of reactants and products in equilibrium systems vary greatly;...
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
Transition State Theory
Transition-state theory, also known as activated-complex theory, provides a molecular-level explanation of reaction rates in both gas-phase and solution-phase reactions. It extends earlier kinetic models by considering the formation of a short-lived, high-energy configuration during a reaction.The progress of a chemical reaction can be represented using a reaction profile, which plots potential energy against the reaction coordinate. As two reactant molecules approach one another, their...
Catalysis
Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...
Heterogeneous Catalysis
Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)

![[(DPEPhos)(bcp)Cu]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)