Pt触媒によるC-C活性化がC-H活性化によって誘発される
Miriam A Bowring1, Robert G Bergman, T Don Tilley
1Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Journal of the American Chemical Society
|August 22, 2013
まとめ
プラチナ ((II) 触媒は,炭化水素に二酸化炭素結合を分裂させ,新しい再配列製品を生み出します. この研究は,C-H結合の活性化によって開始される異常な触媒機構を明らかにしています.
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:
- 炭素-炭素 (C-C) 結合の分裂は,有機化学における根本的な変化である.
- C-C結合活性化のための効率的な触媒方法の開発は,依然として大きな課題です.
研究 の 目的:
- スピロ[ビサイクロ[2.2.1]ヘプト-2-エネ-7,1'-サイクロプロパン]における2つのC-C単一結合の触媒的分裂を調査する.
- この新しい触媒変換のメカニズムを,プラチナ (((II)) 触媒を用いて解明する.
主な方法:
- 炭化水素基板をプラチナ ((II)) 触媒,特に (Me2bpy) PtPh ((NTf2) で処理する.
- NMRスペクトロスコーピーとエレクトロスプレーイオン化質量スペクトロメトリを用いた製品の特徴付け.
- デウテリウムラベルと密度関数理論 (DFT) の計算を含むメカニズム研究.
主要な成果:
- 触媒反応は,基板の2つのC-C単一結合を成功裏に割った.
- 1,2,4,7,7a-pentahydroindeneという驚くべき再編成製品が良好な収量で得られた.
- 証拠は,初期C-H結合の活性化に続いてC-C結合の分裂を含む異常な触媒メカニズムを支持しています.
結論:
- プラチナ (((II) 触媒は,複雑な炭化水素内の複数のC−C結合の分裂を効果的に媒介することができます.
- この反応は,C-H結合の活性化によって開始されたユニークなメカニズムを通して進行し,触媒的なC-C結合の活性化戦略に関する新しい洞察を提供します.
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