活性化されていないアルケンのニオケタライズドアリルボレーション:範囲とメカニズム研究
Stephen R Sardini1, Alison L Lambright1, Grace L Trammel1
1Department of Chemistry , Indiana University , 800 East Kirkwood Avenue , Bloomington , Indiana 47405 , United States.
Journal of the American Chemical Society
|June 12, 2019
まとめ
この研究では,複雑な分子を作るための新しいニッケル触媒によるアリルボレーション法が導入されました. この反応は,高度に置換されたアルケンの有価な炭素-ボロン結合を効率的に合成し,ステレオ選択性および地域選択性に対する制御を提供します.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- アリルボレーション反応はC−C結合形成に不可欠である.
- 制御されたステレオ化学で高度に置換されたアルケンを合成することは依然として困難です.
- 炭素とボロンの結合を作るための効率的な方法の開発は,有機合成に不可欠です.
研究 の 目的:
- ニッケル触媒による新型アリルボレーションの 開発
- 活性化されていないアルケーンとアリルブロミドから複雑な分子合成を可能にします.
- 新しい反応のメカニズムを調査する.
主な方法:
- 様々なアルケンのニッケル触媒化アリルボレーション (単位置換,1,1-非置換,三位置換).
- アリルブロミドとディボロン反応剤を使用した.
- 反応メカニズムを研究するために計算と実験の技術を採用した.
主要な成果:
- 活性化されていない,高度に置換されたアルケンの成功アリルボレーション.
- 四次炭素中心と多用途の炭素-ボロン結合を持つ製品の形成.
- ステレオ選択性や地域選択性に対する制御が実証されている.
- 飽和窒素ヘテロサイクルの合成における応用
結論:
- 開発されたNi-触媒化された方法は,合成的に価値のあるアリルボロン化合物への効率的な経路を提供します.
- この方法論は,重要な薬学的なモチーフの合成に適用できます.
- 機理学的な研究は,反応の異常な反応性と選択性についての洞察を提供します.
関連する概念動画
02:45Acid-Catalyzed Hydration of Alkenes
17.1K
Alkenes react with water in the presence of an acid to form an alcohol. In the absence of acid, hydration of alkenes does not occur at a significant rate, and the acid is not consumed in the reaction. Therefore, alkene hydration is an acid-catalyzed reaction.
17.1K
02:35Acid-Catalyzed Dehydration of Alcohols to Alkenes
23.8K
In a dehydration reaction, a hydroxyl group in an alcohol is eliminated along with the hydrogen from an adjacent carbon. Here, the products are an alkene and a molecule of water. Dehydration of alcohols is generally achieved by heating in the presence of an acid catalyst. While the dehydration of primary alcohols requires high temperatures and acid concentrations, secondary and tertiary alcohols can lose a water molecule under relatively mild conditions.
23.8K
01:17The Scope of Physics
52.5K
Physics is concerned with the interactions of energy, matter, space, and time, in order to discover the underlying mechanisms that underpin all phenomena. The word "physics" comes from the Greek word "phúsis", which means nature. Physics seeks to comprehend the natural world around us at its most fundamental level. It emphasizes the use of quantitative laws to do this, which could be valuable in other fields that want to push the performance boundaries of present...
52.5K
02:29Nomenclature of Alkenes
15.1K
The IUPAC naming system for alkenes replaces -an- with -en- in the corresponding parent alkanes. Accordingly, a simple alkene replaces the -ane suffix of the alkane with -ene.
As per the IUPAC rules, the longest carbon chain containing the maximum number of double bonds is identified as the parent chain and is numbered such that the doubly bonded carbon atoms receive the lowest possible numbers. The location of the double bond is indicated by the number of its first carbon atom. In branched...
As per the IUPAC rules, the longest carbon chain containing the maximum number of double bonds is identified as the parent chain and is numbered such that the doubly bonded carbon atoms receive the lowest possible numbers. The location of the double bond is indicated by the number of its first carbon atom. In branched...
15.1K
02:01Isomerism in Alkenes
14.7K
Alkenes like 1-butene and 2-butene exhibit constitutional isomerism, as they differ in the position of the double bond. Further, 2-butene exhibits stereoisomerism and exists as two distinct compounds differing in spatial arrangement.
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
14.7K
02:46Halogenation of Alkenes
18.5K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
18.5K