アルケンの触媒的,ダイアステロ選択的1,2-二化
Steven M Banik1, Jonathan William Medley1, Eric N Jacobsen1
1Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
Journal of the American Chemical Society
|April 6, 2016
まとめ
この研究では,フッ素とアリルヨウ素触媒を用いた酸化剤を用いたアルケンの二酸化のための直接触媒法が導入されます. このプロセスは,様々なアルケンのタイプに適用可能な,高いステレオ選択性を持つ近隣二酸化物を生成します.
科学分野:
- 有機化学
- 化化学
- カタリシス
背景:
- アルケンの1,2-二酸化化は合成化学における重要な変換である.
- 既存の方法はしばしば厳しい条件を必要とし,広く適用できない.
研究 の 目的:
- アルケンの直接的,触媒的,多用途の方法を開発する.
- 近隣の二酸化物形成において高い二酸化物選択性を達成する.
主な方法:
- 核性フッ素と酸化剤を使った
- アリルヨウ素触媒を直接の二酸化反応に使用した.
- 様々なアルケンの置換パターンの適用性を調査した.
主要な成果:
- 各種のアルケンの直接触媒的1,2-二化が達成された.
- 一般的に,高いダイアステレオ選択性を持つ製品が得られた.
- 多様な置換パターンを持つアルケンの適用性が実証されている.
結論:
- 開発された方法は,近隣の二酸化物への効率的な経路を提供します.
- 特定の基板のステレオ誘導には,アンキメリックアシスタンス経路が関与しています.
- この触媒的アプローチは,化反応のための合成ツールキットを拡張します.
関連する概念動画
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
3.9K
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
3.9K
Halogenation of Alkenes
21.0K
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.
21.0K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
13.3K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
13.3K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
4.0K
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...
4.0K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
5.1K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
5.1K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
5.3K
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
5.3K


