リモートエステルグループは,非対称な水素化によるラセミアリファティックアルコールの効率的な動的解離につながります
Xiao-Hui Yang1, Ke Wang, Shou-Fei Zhu
1State Key Laboratory and Institute of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, China.
Journal of the American Chemical Society
|December 2, 2014
まとめ
新しい方法は,ラセミアルコールの効率的な動的解像度のためにキラルイリジウム触媒を使用しています. この環境に優しいプロセスは,非常に低い触媒濃度でも,高いエナチオセレクティブ性を持つキラルヒドロキシエステルとダイオルを生成します.
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
- アシンメトリック・シンセシス
背景:
- ラセミアルコールの運動解像度は,キラル化合物の合成に不可欠である.
- 既存の方法は,しばしば厳しい条件を必要とし,または効率が欠けている.
- 効率的で環境に優しい解決方法の開発は,継続的な課題です.
研究 の 目的:
- ラセミア・アリファティック・アルコールの運動解像度に関する高効率の方法を開発する.
- これを達成するには,ヒドロキシル基を変化させずに.
- 非対称合成のための新しい触媒システムを活用する.
主な方法:
- 触媒としてキラルイリジウム複合体を用いる.
- 遠隔エステル群媒介による水素化を活用する.
- ラセミアアリファティックアルコールで運動解像度を行う.
主要な成果:
- ラセミックアリファティックアルコールの非常に効率的な動的解像度を達成しました.
- 生成されたキラル型δ-アルキル-δ-ヒドロキシエステルとδ-アルキル-1,5-ダイオール.
- 良い収穫量と高いエナチオ選択性を得ました.
- 非常に低い触媒負荷 (0.001 mol %) で実証された有効性.
結論:
- アルコールを動的分解するための強力で環境に優しい方法が確立されています.
- この方法は,高い効率とエナチオセレクティブ性を提供します.
- このアプローチは,有機合成におけるキラルな構成要素にアクセスするのに価値があります.
関連する概念動画
Stereochemical Effects of Enolization
2.9K
The chiral α-carbon of the carbonyl compound is the stereocenter of the molecule. As shown in the figure below, when such a carbonyl compound undergoes racemization under an acidic or basic condition, an achiral enol is formed.
2.9K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
4.1K
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...
4.1K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
19.2K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
19.2K
Regioselectivity of Electrophilic Additions-Peroxide Effect
12.2K
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
12.2K
Preparation of Alcohols via Substitution Reactions
8.4K
Overview
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
8.4K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
10.4K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
10.4K


