三座標銅 ((II) アリル:C−O結合形成における重要な中間物質
Subrata Kundu1, Christine Greene1, Kamille D Williams1
1Department of Chemistry, Georgetown University , Box 571227-1227, Washington, D.C. 20057, United States.
Journal of the American Chemical Society
|June 8, 2017
まとめ
新しい銅 (II) アリル複合体は合成され,特徴づけられました. これらの中間物質は窒素酸化物とフェノラートアニオンと反応し,独特の銅媒介経路を通じてC-N結合形成とダイアリルエーテル合成を可能にします.
科学分野:
- 有機金属化学
- カタリシス
- 合成化学
背景:
- 銅 (II) アリル種は,銅触媒によるクロスカップリング反応において重要な中間物質である.
- その構造と反応性を理解することは 新しい合成方法論の開発の鍵です
研究 の 目的:
- 新しい3座標の銅 (II) アリル複合体を合成し,特徴づけること.
- 窒素酸化物やアニオンのような小さな分子とこれらの複合体の反応性を調べる
- C−N結合形成とダイアリルエーテル合成のメカニズムを解明する.
主な方法:
- 銅 (II) アルコシドの合成とB (C6F5) 3との反応
- 結晶学,光譜学 (NMR,EPR),密度関数理論 (DFT) による研究.
- ガス状の酸化窒素 (NO) とフェノ酸アニオン (PhO-) との反応
主要な成果:
- ベータ・ディケチミネート・リガンドで支えられた新しい3座標銅 ((II) アリルの形成.
- Cu (II) オルガノメタリック複合体のユニークな幾何学および電子構造を明らかにする特徴.
- NOでC-N結合が形成され, [Cu]{eta}{2) -ONC6F5が得られる.
- ディアリルエーテル (PhO-C6F5) をフェノラートとの反応から直接合成し,Cu (I) と一時的なCu (III) 種を形成する.
結論:
- 合成された銅 (II) アリル複合体は,有機金属変換における多用途の中間物質である.
- この研究は,銅媒介C-N結合とダイアリルエーテル形成に関する機械的洞察を提供します.
- この研究は,溶解における銅 (II) オルガノメタリック化合物の反応の範囲を拡大する.
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