活性と選択性プロファイルが最適化された実用的な新型シルイロキシ基アルキン転移触媒
Johannes Heppekausen1, Robert Stade, Richard Goddard
1Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim/Ruhr, Germany.
Journal of the American Chemical Society
|August 12, 2010
まとめ
新しいモリブデンアルキリジンの複合体とトリフェニルシラノ酸リガンドは,汎用的なアルキン転移反応を可能にします. これらの触媒は,高機能群耐性を提供し,環境温度下でも簡単に操作できます.
科学分野:
- 有機金属化学 有機金属化学
- カタリシス カタリシス カタリシス
- オーガニック・シンセシス オーガニック・シンセシス
背景:
- アルキンメタテシスは,炭素-炭素結合を形成するための有機合成における重要な反応である.
- 非常に反応性があり,機能群に耐性があり,簡単に操作できる触媒の開発は,依然として重要な課題です.
研究 の 目的:
- アルキンメタテシスのための新しいモリブデンアルキリディン複合体を開発する.
- これらの新しい複合体の触媒的活動,安定性,範囲を調査する.
- 反応条件を最適化して,効率を上げ,適用範囲を広げる.
主な方法:
- トリフェニルシラノ酸リガンドを含むモリブデンアルキリジンの複合体の合成.
- モリブデンニトリド前駆体から活性種を in situ で生成する.
- 1,10-フェナントロリンと複合し,空気に安定したアドクトを形成する.
- 様々な分子間および分子内アルキンメタテシス反応における触媒試験.
- 構造分析のための分子シートとX線結晶学を用いた最適化.
主要な成果:
- トリフェニルシラノラートリガンドは,モリブデンアルキリジンの触媒に優れた反応性と機能群耐性を与えます.
- 空気に安定したフェナントロリン添加物は,触媒作用のために容易に活性化することができます.
- 反応は環境温度で効率的に進行し,分子シートを使用すると,有意な収穫量と速度の改善が観察されます.
- 生物活性天然製品の合成に成功する応用は,幅広い範囲を示しています.
結論:
- トリフェニルシラノ酸リガンドを含む新型モリブデンアルキリジンの複合体は,新世代の高効率のアルキン転移触媒を代表しています.
- これらの触媒は,操作の簡単さ,広範な適用性,および耐久性により,実践者にとって実用的な選択を提供します.
- 分子シートの使用は反応効率を高め,より穏やかな反応条件を可能にし,基板要件を簡素化します.
関連する概念動画
Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
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.
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...


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