強いアルキンメタテシス 空気によって触媒化 安定したd2 Re(V) アルキリジン複合体
Mingxu Cui1, Wei Bai1, Herman H Y Sung1
1Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Journal of the American Chemical Society
|July 17, 2020
まとめ
この研究は,触媒性アルキン転移のための最初の非d0アルキリジン・レニウム複合体を導入する. 堅固な触媒は,湿った溶媒でも,多様な内部アルキンの同位分子を効率的に媒介する.
科学分野:
- 有機金属化学
- キャタリシス
- 有機合成
背景:
- アルキンの転化は有機合成における重要な変化である.
- 新しい触媒の開発は,アルキンの転移の範囲と効率を拡大するために不可欠です.
研究 の 目的:
- よく定義された非d0アルキリジン複合体によって媒介された触媒性アルキン転移反応の最初の例を報告する.
- d2 Re(V) アルキリジン複合体の触媒活性と安定性を調査する.
主な方法:
- 新しいd2 Re(V) アルキリジン複合体 (Re4) の合成と特徴付け
- 内アルキンのホモメタテシスの触媒としての複合体の評価.
- 活性化剤の安定性と基板の適用範囲の評価,機能群の耐性を含む.
主要な成果:
- d2 Re(V) アルキリジン複合体 Re4 は,内部アルキンの同位分子を効果的に触媒化する.
- 触媒はアルコール,アミン,カルボキシル酸などの機能群を許容する幅広い基板範囲を示します.
- 触媒は空気,水分,熱に対して優れた安定性を示し,湿った溶剤で効果的に機能します.
結論:
- よく定義された非d0アルキリジンの複合体は,アルキンの転移のための新しい触媒のクラスを表します.
- 開発されたレニウム触媒は,広範な機能群耐性を持つアルキン転移のための堅牢で汎用的なプラットフォームを提供します.
関連する概念動画
Preparation of Alkynes: Alkylation Reaction
11.8K
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.
11.8K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.8K
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.
8.8K
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
2.7K
Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.
2.7K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
20.3K
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.
20.3K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
2.2K
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.
2.2K
Preparation of Alkynes: Dehydrohalogenation
17.6K
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
17.6K


