パラジウム/ノルボネン協同触媒による多機能の1,2-アザボリンへの迅速かつモジュラーなアクセス
Shinyoung Choi1, Guangbin Dong1
1Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|March 29, 2024
まとめ
この研究では,C3およびC4の位置で1,2-アザボリンを機能停止させるための新しいパラジアム/ノルボレン (Pd/NBE) 触媒法が導入されています. このアプローチにより,広範囲の機能群耐性を有する複雑な,高度に置換された1,2-アザボリンを合成することができる.
科学分野:
- 有機化学
- カタリシス
- ヘテロサイクル化学
背景:
- 1,2-アザボリンはベンゼンの重要なBNイソステルで,様々な用途がある.
- 既存の方法は,選択的なC4機能化と高度に置換されたデリバティブへのアクセスで課題に直面しています.
研究 の 目的:
- 1,2-アザボリンのC3とC4の機能低下のための迅速でモジュール化された方法を開発する.
- 選択的な機能化と代替装置の制限を克服する.
主な方法:
- パラジアム/ノルボネン (Pd/NBE) の協力触媒を用いる.
- 主要な有効成分としてC2アミド置換ノルボネン (NBE) を使用した.
- 様々な3イオド-1,2アザボリンや様々なアルケーン/核性物質を含む研究対象の基板.
主要な成果:
- 1,2-アザボリンの選択的C3およびC4機能低下を達成した.
- 広範な機能群の耐性と成功したオーソアリレーションと初期オーソアルキレーションを証明した.
- アルケーンと核愛素でipso C3の機能化が可能になった.
- ヘクサ置換された1,2-アザボリンを形成するためのスケーラビリティと,その後のポスト機能化を示した.
結論:
- 開発されたPd/NBE共同触媒は,複雑な1,2-アザボリン誘導体を合成するための強力でモジュール式な戦略を提供します.
- この方法は,高度に置換された1,2-アザボリンのアクセシビリティを大幅に向上させ,合成の有用性を拡大します.
さらに関連する動画
![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
25.4K
07:36Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
8.0K
関連する概念動画
01:26Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
3.5K
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...
3.5K
02:36Regioselectivity and Stereochemistry of Hydroboration
8.1K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.1K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.3K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.3K
01:28Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation
4.5K
Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...
4.5K
01:22Preparation of 1° Amines: Azide Synthesis
3.9K
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
3.9K
01:18Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
2.2K
Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
2.2K