ロージウム触媒によるアルケンのシンカルボアミネーション
Tiffany Piou1, Tomislav Rovis1
1Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Nature
|October 28, 2015
まとめ
この研究は,アルケンのカルボアミン化のための新しいロジウム触媒反応を導入する. この方法は,炭素-炭素と炭素-窒素結合の,前例のない分子間,ステレオ選択合成を達成します.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- アルケンは有機合成における重要なプロキラル構成要素である.
- アルケンの機能不全は複雑な分子構造を作るための鍵です.
- 既存のステレオセレクティブアルケンの機能化には,同時に炭素-窒素結合の形成がない.
研究 の 目的:
- アルケンの分子間,ステレオ選択的二機能化のための新しい方法を開発する.
- アルケンの間の炭素と炭素と窒素の結合を同時に形成する.
- アミンを含むアサイクリック分子のための新しい合成経路を確立する.
主な方法:
- エノキシフタリミドを用いたアルケンのロジウム触媒カルボアミネーション.
- バイデント・ディレクター・グループのインサイト生成
- 反応性の制御のための新しいサイクロペンタディエニルリガンドの利用.
主要な成果:
- アルケンの分子間,シン-ステレオ選択カルボアミン化が成功しました.
- 単一の反応でアルケンの間でC-CとC-Nの両方の結合の形成.
- 機能化されたアルケンを合成するための新しい戦略を示した.
結論:
- 開発されたロジウム触媒反応は,アルケンの二機能化のための新しい経路を提供します.
- この方法論は,複雑なアミンを含む分子の収束性およびステレオ選択的合成を可能にします.
- ステレオ選択的有機合成のためのツールキットを拡張します.
さらに関連する動画
関連する概念動画
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.5K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
9.5K
01:15α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
3.9K
The method to achieve α-brominated carboxylic acids using a mixture of phosphorus tribromide and bromine is known as the Hell–Volhard–Zelinski reaction. The reaction is catalyzed by phosphorus tribromide, which can be used directly or produced in situ from red phosphorus and bromine. The mechanism comprises PBr3 catalyzed conversion of acid to acid bromide and hydrogen bromide. The acid bromide enolizes to its enol form in the presence of HBr. The nucleophilic enol attacks the...
3.9K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
2.4K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
2.4K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
21.9K
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.
21.9K
01:27Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
3.1K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
3.1K
02:27Preparation of Alkynes: Alkylation Reaction
12.6K
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.
12.6K