カルバゾールとダイアリアミンのCu触媒性エアロビック酸化N-N結合,選択的クロスカップリングを含む
Michael C Ryan1, Joseph R Martinelli2, Shannon S Stahl1
1Department of Chemistry , University of Wisconsin-Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States.
Journal of the American Chemical Society
|July 11, 2018
まとめ
新しい銅触媒法により,炭酸塩とダイアリアミンをN-N結合製品に酸素酸化で二酸化することができる. この反応は顕著な選択性を示し,可逆的な中間体を通して熱力学的に安定したクロスカップリング製品を好む.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- カーバゾールとダイアリアミンは,窒素を含む重要なヘテロサイクルである.
- 酸化二酸化反応は,C-NおよびN-N結合の形成に不可欠である.
- これらの変換のための選択的触媒的方法の開発は依然として課題です.
研究 の 目的:
- カルバゾールとダイアリアミンの有酸素酸化二酸化のための新しい銅触媒法を開発する.
- これらの基板間のクロスカップリング反応の選択性を調査する.
- 観察された選択性の背後にあるメカニズムを明らかにする.
主な方法:
- N,N-ディメチラミノピリジンと銅ブロミド二甲酸塩触媒を使用した.
- 1 atmの酸素と60~80°Cの温度で使用するエアロビック条件.
- 標準的な有機合成技術とスペクトロスコーピック方法を用いて分析した反応産物.
主要な成果:
- カルバゾールとダイアリラミンの効率的なN-N結合により,ビカルバゾールとテトラアリルヒドラジンが生成される.
- カーバゾールとダイアリアミンの間のクロスカップリング反応において,異常に高い選択性を示した.
- 選択性の鍵として,熱力学的に安定した製品を好む可逆性テトラアリルヒドラジン形成を特定した.
結論:
- 温和で効率的なCu触媒有酸素二酸化法が確立されている.
- この反応は,可逆的な中間メカニズムによって誘導されるクロスカップリング製品に対する優れた選択性を示す.
- この研究は,材料科学と医薬品化学における潜在的な応用を持つN-N結合ヘテロサイクルへの貴重な合成経路を提供します.
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