C-H活性化と陽子移転がアルケンの転化活動を開始する
Ka Wing Chan1, Erwin Lam1, Vincenza D'Anna2
1ETH Zürich , Department of Chemistry and Applied Biosciences , Vladimir Prelog Weg 1-5 , CH-8093 Zurich , Switzerland.
Journal of the American Chemical Society
|August 16, 2018
まとめ
トングステン (IV) -オクソ複合体はアルケンの転移反応を活性化する. このプロセスは,アリルC-H結合を必要とし,陽子転送メカニズムを含み,アクティブなボルンガム (VI) 種を生成します.
科学分野:
- 有機金属化学
- カタリシス
- 有機合成
背景:
- アルケンの転化は有機合成における重要な反応である.
- 高値のボルンガムアルキリデンは中介物質として知られている.
- 低値のボルンガム前触媒の役割は不明である.
研究 の 目的:
- 低値タングステンの前触媒の活性化メカニズムを調査する.
- 新しい ((IV) -オクソ複合体を合成し,特徴づけます.
- アルケンの転移の開始経路を決定する.
主な方法:
- トングステン (IV) -オクソビサルコキシド複合体の合成
- ルイス酸 (B(C6F5) 3を用いた活性化.
- 動力学研究,デュテリウム同位体ラベル付け,そしてDFT計算.
主要な成果:
- トングステン (IV) -オクソ複合体はアルケンの転移活性が高い.
- アリルC-Hの活性化が必須である.
- 主要な運動同位体効果が観察された.
- DFTの計算で 陽子伝達メカニズムが解明されました
結論:
- トングステン (IV) -オクソ複合体は,アルケンの転化に有効な前触媒として機能する.
- 開始には,アリルC-H結合の活性化と,ルイス酸/塩基によるプロトン転送が含まれます.
- このメカニズムは活性 (VI) 種を生成します.
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