ニッケル触媒によるアルケンの還元性二酸化炭素機能化
Andrés García-Domínguez1, Zhaodong Li1, Cristina Nevado1
1Department of Chemistry, University of Zurich , Winterthurerstrasse 190, Zurich CH 8057, Switzerland.
Journal of the American Chemical Society
|May 11, 2017
まとめ
この研究は,アルケンの二酸化炭素機能化のための新しい3つの成分反応を導入する. ニッケル触媒とTDAE還元剤は,穏やかな条件下で新しい炭素-炭素結合を生成します.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- アルケンの機能化は有機合成において極めて重要です.
- C−C結合形成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:
- アルケンの新しい分子間,三要素の還元性二カルボ機能化を提示する.
- Csp3-Csp3 と Csp3-Csp2 の結合を形成する方法を確立する.
主な方法:
- ニッケル (Ni) 触媒を用いる.
- テトラキス・ディメチラミノエチレン (TDAE) を末端減量剤として使用する.
- 2つの異なる電ophilesの連続的な活性化.
主要な成果:
- 複数の π システムの二酸化炭素機能化に成功した.
- 直接Csp3-Csp3とCsp3-Csp2の結合を形成する.
- 軽度な反応条件下で観察された優れた選択性.
結論:
- 開発された方法は,アルケンの機能化のための汎用的な経路を提供します.
- Ni/TDAEシステムは効率的な触媒的アプローチを提供します.
- この研究は 複雑な有機分子を作るための ツールキットを拡張します
関連する概念動画
Alkenes 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
Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids
4.5K
Although it is possible to reduce a carboxylic acid to an aldehyde, strong reducing agents, like lithium aluminum hydride (LAH), prohibit a controlled reduction, instead causing the generated aldehyde to instantly over-reduce to a primary alcohol.
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H]...
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H]...
4.5K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.9K
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...
3.9K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.2K
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.
9.2K
Alcohols from Carbonyl Compounds: Reduction
12.7K
Reduction is a simple strategy to convert a carbonyl group to a hydroxyl group. The three major pathways to reduce carbonyls to alcohols are catalytic hydrogenation, hydride reduction, and borane reduction.
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
12.7K
Aldehydes and Ketones to Alkanes: Wolff–Kishner Reduction
5.9K
Wolff–Kishner reduction involves converting aldehydes and ketones to alkanes using hydrazine and a base. The reaction converts a carbonyl group to a methylene group. The method was independently discovered by N. Kishner in 1911 and L. Wolff in 1912. The reduction is carried out in high-boiling solvents such as ethylene glycol and diethylene glycol because heat is required to deprotonate the N–H proton in one of the reaction steps. ...
5.9K


