アルデヒドのホモアリルボレーションとホモクロチルボレーション
1Department of Chemistry MS 015, Brandeis University, Waltham, Massachusetts 02454-9110, USA.
Journal of the American Chemical Society
|October 22, 2011
まとめ
新しいサイクロプロパネートアリルボレーション法では,アルデヒドにホモアリル断片を効率的に加え,ビショモアリルアルコールを生成します. この反応は,メチル置換製品に対して高いステレオ選択性を提供し,有機合成に有用である.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成方法論 合成方法論
- ステレオセレクティブ合成
背景:
- アルデヒドの機能化は,有機合成において極めて重要です.
- 複雑なアルコール構造を作り出すための効率的な方法の開発は,依然として重要な課題です.
研究 の 目的:
- アルデヒドにホモアリル断片を加えるための新しい方法について説明する.
- この反応のステレオ化学的結果を調査するために.
主な方法:
- サイクロプロパン酸アルリボレーション反応剤を用いて.
- これらの反応剤をフェニルボロン二塩化物 (PhBCl2) の存在下でアルデヒドと反応させる.
- 光学的に活性な原材料を使用して,enantioselectivityを評価する.
主要な成果:
- ビショモアリルアルコールの高収量が得られた.
- サイクロプロパン酸のシスおよびトランスクロチル反応剤は,選択的に1,3-アンチおよび1,3-シンメチル置換アルコールを生成した.
- 光学的に活性な反応剤からEで置換された製品について,優れたエナティオメール比 (97:3 er) が観察されました.
結論:
- 開発された方法は,ビショモアリルアルコールへの簡単な経路を提供します.
- 反応は,ジマーマン-トラクスラー移行状態と一致する高いダイアステレオ選択性およびエナチオ選択性で進行します.
- この方法論は,複雑な有機分子の立体選択合成のためのツールキットを拡張します.
関連する概念動画
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.
C–C Bond Formation: Aldol Condensation Overview
Aldol condensation is an important route in synthetic organic chemistry used to generate a new carbon–carbon bond under basic or acidic conditions. The aldol condensation reaction presented in Figure 1 constitutes an aldol addition reaction followed by the dehydration process.
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...
Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes
Aldehydes and ketones are prepared from alcohols, alkenes, and alkynes via different reaction pathways. Alcohols are the most commonly used substrates for synthesizing aldehydes and ketones. The conversion of alcohol to aldehyde, which involves the oxidation process, depends on the class of the alcohol used and the strength of the oxidizing agent. For instance, primary alcohol will form an aldehyde when treated with a weak oxidizing agent; however, it gets over-oxidized to a carboxylic acid in...
Base-Catalyzed Aldol Addition Reaction
As depicted in Figure 1, base-catalyzed aldol addition involves adding two carbonyl compounds in aqueous sodium hydroxide to form a β-hydroxy carbonyl compound.


