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銅触媒 sp³ アシル保護フェノールによるC-Hエーテル化

Tolani K Salvador^1,2, Charles H Arnett¹, Subrata Kundu¹

¹Department of Chemistry, Georgetown University , Box 571227-1227, Washington, D.C. 20057, United States.

Journal of the American Chemical Society

|December 14, 2016

まとめ

この研究では,保護されたフェノールからアルキルアリルエーテルを効率的に生成するC-Hエーテル化のための新しい銅触媒法が導入されています. この反応は,ステリカルに阻害された三次性C−O結合を形成することを好む.

科学分野:

有機化学
カタリシス
合成方法論

背景:

アチル保護フェノール (AcOAr) は有機合成における一般的な前体である.
C-H機能化は,複雑な分子への直接的な経路を提供し,機能化前のステップを最小限にします.
銅の触媒は,C-H活性化と結合形成のためにますます利用されています.

研究の目的:

新しい銅触媒 sp3 C-H エステル化反応を開発する.
様々な基質との反応の範囲と選択性を探求する.
銅介質を含む触媒機構を解明する.

主な方法:

乙二キセチミナート触媒を用いたエーテル化反応.
酸化剤としてターチブチル水酸化物 (tBuOO tBu) を使用した.
サブストラット (R-H) での初次,二次,三次C-H結合の機能化を調査した.

主要な成果:

AcOArとR-Hから様々なアルキルアリルエーテル (R-OAr) を合成しました.
C-OAR債券の形成を阻害する選択性を示した.
機械学的研究では,C-O結合形成に銅 ([CuII]-OAr) フェノラートが関与していた.

結論:

保護されたフェノールの効率的な銅触媒 sp3 C-H エステル化を開発した.
この反応は,ステリカルに要求されるアルキルアリルエーテルへの選択的な経路を提供します.
提案されたメカニズムは,トランスエステル化によって形成された主要な銅 (II) の中間物質を含んでいる.

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