![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)
ニッケル触媒による非対称クマダクロスカップリング
Meredith S Eno1, Alexander Lu1, James P Morken1
1Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Journal of the American Chemical Society
|June 9, 2016
まとめ
この研究では,サイクル硫酸塩とグリニャード反応剤を用いたニッケル触媒によるエナチオセレクティブ・クロスカップリングを導入する. この方法は,新しいキラルセンターを持つ複雑な分子を効率的に作成し,非対称合成を進める.
科学分野:
- 有機化学
- 非対称な触媒
背景:
- 循環硫酸は有機合成における多用途の前駆体である.
- 薬の発見と材料科学において,キラル三次炭素センターを作るための効率的な方法を開発することが重要です.
研究 の 目的:
- ニッケル触媒による新種のエナチオセレクティブ・クロスカップリング反応を開発する.
- シンメトリックな環状硫酸塩とアロマティックなグリナード反応剤を用いて,非シンメトリックな三次炭素中心の分子を合成する.
主な方法:
- ニッケル触媒を用いて交互結合反応を行う.
- 代替サイクル硫酸塩とアロマティックグリナード反応剤の範囲を使用しています.
- 反応経路の解明のためのメカニズム的研究を行う.
主要な成果:
- サイクル硫酸とグリナード反応剤の間の有効なエナンチオセレクティブ・クロスカップリングを達成した.
- 様々な代用された循環硫酸で,広範な基板範囲を証明した.
- アシンメトリックな三次炭素中心を含む製品が成功して生成された.
結論:
- 開発されたニッケル触媒反応は,非対称合成のための強力な新しい経路を提供します.
- この反応は,ステレオインバーティブSN2のような酸化添加機構によって進行する.
- この方法論は複雑なキラル分子にアクセスするための大きな可能性を秘めています.
関連する概念動画
02:26Preparation and Reactions of Sulfides
5.9K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
5.9K
01:27Aldol Condensation with β-Diesters: Knoevenagel Condensation
4.0K
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.
4.0K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
2.4K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
2.4K
02:23SN2 Reaction: Stereochemistry
12.5K
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
12.5K
01:27Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview
2.3K
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
2.3K
00:56Crossed Aldol Reaction Using Strong Bases: Directed Aldol Reaction
2.9K
The reaction between two different carbonyl compounds comprising α hydrogen in the presence of a strong base like lithium diisopropylamide (LDA) to form a crossed aldol product is known as a directed aldol reaction. The directed aldol reaction is depicted in Figure 1.
2.9K