オレフィンイソメリゼーションとヒドロシル化触媒は,ルイス酸性オーガノフッロフォスフォニウム塩によるものです
Manuel Pérez1, Lindsay J Hounjet, Christopher B Caputo
1Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
Journal of the American Chemical Society
|November 22, 2013
まとめ
新しいオルガノフッロフォスフォニウム塩は,強力なルイス酸として作用し,オレフィンイソメリゼーション,ポリメリゼーション,水酸化反応を効率的に触媒化する. これらの発見は,有機合成における新しい触媒応用への道を開く.
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
- フロアンの化学的性質
背景:
- オーガノフッロフォスフォニウム塩は,そのユニークな電子特性のために調査されています.
- フォスフォニウム塩のルイス酸性は,しばしば特定の軌道相互作用と関連しています.
研究 の 目的:
- 新型オーガノフルオロフォスフォニウム塩を合成し,特徴づけること.
- これらの塩のルイス酸性および触媒活性を調査するために.
- 触媒的応用に伴う反応機構を解明する.
主な方法:
- 異なるフェニルおよびペンタフローロフェニル置換剤を用いたオーガノフローロフォスフォニウム塩の合成.
- オレフィンイソメリゼーション,カチオンポリメリゼーション,フライデル・クラフトス・ディメリゼーションにおける触媒試験.
- オレフィンとアルキンの水溶化は,水溶を用いて行われます.
- 反応機構を理解するための実験的および計算的研究.
主要な成果:
- 合成された塩は,低地にあるの σ* 軌道により,重要なルイス酸性を示す.
- 1 - ヘクセンの2 - ヘクセンのイソメリゼーションに効率的な触媒が観察されました.
- イソブチレンのカチオンのポリメリゼーションと1,1-ディフェニルエチレンの二酸化を成功裏に触媒化しました.
- オレフィンとアルキンは,ヒドロシランの存在下でアルキルシランに効率的な水溶化を行いました.
結論:
- オルガノフッロフォスフォニウム塩は,様々な有機変異のための効果的なルイス酸触媒である.
- 触媒的活動は,フォスフォニウムカチオンのユニークな電子構造に起因する.
- このメカニズムは,連続した活性化と1,2-添加,特に水溶化反応において行われる.
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