なぜBINOLベースのモノフォスフィートは,Rh触媒による非対称オレフィン水素化の効率的なリガンドなのか?
Manfred T Reetz1, Andreas Meiswinkel, Gerlinde Mehler
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim/Ruhr, Germany. reetz@mpi-muelheim.mpg.de
Journal of the American Chemical Society
|July 21, 2005
まとめ
この研究は,キラル・フォスフィート・リガンドが,ロジウム触媒によるオレフィン水素化における高いエナチオセレクティビティを生成する方法を明らかにしています. 古典的な方法とは異なるロック&キーメカニズムが,ステレオ化学的結果を決定する.
科学分野:
- 有機金属化学 有機金属化学
- アシンメトリック・カタリシス
- 機械学研究 機械学研究
背景:
- BINOL由来のモノデント酸リン酸塩を用いたロジウム触媒によるオレフィン水素化は,効率的な合成経路を提供します.
- 高いエナチオセレクティブ性 (90-99% ee) が頻繁に観察されていますが,その基礎となるメカニズムは依然として十分に理解されていません.
研究 の 目的:
- モノデント酸ホスフィットによるRh触媒によるオレフィン水素化における高いエナントイオセレクティビティの背後にあるメカニズムを解明する.
- 立体化学制御におけるリガンド協調と中間形成の役割を調査する.
主な方法:
- 前触媒の特徴化のための核磁気共鳴 (NMR) スペクトロスコーピー.
- 非線形効果の分析を含む運動学的研究.
- 反応経路をモデル化するための密度関数理論 (DFT) 計算.
主要な成果:
- 特性分析により,2つのモノデント酸リン酸リガンドがロジウムに結合していることが確認された.
- 動力学とDFTの研究は"ロック&キー"メカニズムを支持した.
- ロジウム-オレフィン複合体の熱力学は,ダイアステロエメリック中間物質を介してステレオ化学的結果を決定した.
結論:
- ダイアステロエーマー中間形成によって駆動される"ロック&キー"メカニズムは,高いエナチオセレクティブ性を説明します.
- このメカニズムは,キラルディフォスフィンによる伝統的なRh触媒化水素化で観察される"アンチロック&キー"メカニズムと対照的です.
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