ケトンとアルデヒドの直接アルドール反応のための非常に効率的な有機触媒 [修正]
Zhuo Tang1, Zhi-Hua Yang, Xiao-Hua Chen
1Key Laboratory for Asymmetric Synthesis and Chirotechnology of Sichuan Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041, China.
Journal of the American Chemical Society
|June 23, 2005
まとめ
チラルL-プロリンアミドは,アルドールの直接反応を効果的に触媒化する. 電子を取り除くグループは,触媒の性能を高め,様々なアルデヒドおよびケトンから高度にエナチオセレクティブのβ-ヒドロキシケトンを生成します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- アシンメトリック・カタリシス
背景:
- 直接的なアルドル反応は,有機合成における重要な炭素-炭素結合形成反応である.
- 非対称的なアルドール反応のための効率的で選択的な触媒の開発は,依然として重要な課題です.
研究 の 目的:
- 直接のアルドル反応のための有機触媒としての新しいL-プロリンアミドを合成し,評価する.
- 代替剤の電子特性の触媒活性およびエナチオ選択性に対する影響を調査する.
主な方法:
- ベータアミノアルコールから派生したキラルL-プロリンアミドの合成.
- 4-ニトロベンザルデヒドとアセトンの間の直接アルドール反応における触媒の評価.
- サイクロヘクサノンとサイクロペンタノンを含むさまざまなアルデヒドとケトンで触媒の性能を試験する.
主要な成果:
- 電子を取り除くグループを持つL-プロリンアミドは,優れた触媒活性とエナチオセレクティブ性を示した.
- 触媒4g (2 mol %) は,アセトンとブタノンの様々なアルデヒドのアルドール反応を効率的に促進し,96%から>99%のエナティオメール過剰 (ee) を達成しました.
- 抗アルドール剤に対する高ダイアステロ選択性 (95/5) は,サイクロヘキサノンで観察され,優れたエナチオ選択性 (93% ee) は,サイクロペンタノンで得られた.
結論:
- チラルのL-プロリンアミドは,直接的なアルドール反応のための効果的な有機触媒である.
- 置換物の電子的性質は,触媒効率とステレオ選択性に大きな影響を及ぼします.
- これらの触媒は,高度にエナチオメリックに濃縮されたβ-ヒドロキシケトンへの有望な経路を提供します.
関連する概念動画
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
Similar to water, alcohols can add to the carbonyl carbon of the aldehydes and ketones. The addition of one molecule of alcohol to the carbonyl compound forms the hemiacetal or half acetal. As depicted below, in a hemiacetal, the carbon is directly linked to an OH and OR group.
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
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...
Catalysis
Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...


