ハイドラジドは,アルケンの水素アミナ化とアミノカルボニレーションのための調節可能な反応剤として用いられる
Jean-Grégoire Roveda1, Christian Clavette, Ashley D Hunt
1Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K1N 6N5.
Journal of the American Chemical Society
|June 10, 2009
まとめ
ベンゾ酸ヒドラジドは,高温で分子内ヒドロアミナ化を起こします. 反応剤の構造の変化により,アミノカルボニル化製品が生成され,一つの反応はステレオ特異性を示した.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成化学 合成化学とは
背景:
- ベンゾ酸ヒドラジドは,熱的に安定した反応剤です.
- 高温でのそれらの反応性は,合成変換に興味があります.
研究 の 目的:
- ベンゾ酸ヒドラジドの高温反応を調査するために.
- 反応結果に対する反応剤構造の影響を調べる.
主な方法:
- ベンゾ酸ヒドラジドを120~235°Cの温度で加熱する.
- 密度関数理論 (DFT) の計算を用いた計算分析.
- ベンゾ酸ヒドラジド反応剤の構造変化.
主要な成果:
- 内部分子ヒドロアミネーション製品は,ベンゾ酸ヒドラジド (R=Ph) から120~235°Cで得られた.
- ハイドラジニウムイライド中間体による陽子の移転に続く協調したコップ型水素アミネーションが提案されています.
- アミノカルボニレーション製品は,200°Cでの改変反応剤 (R = Ot-BuまたはNH ((2)) で好まれた.
- R = NH ((2) とのアミノカルボニレーション反応はステレオ特異であることが判明しました.
結論:
- ベンゾ酸ヒドラジドは,高温でユニークな反応性を発揮します.
- 反応剤の構造が反応経路を決定し,水酸化アミネ化またはアミノカルボニル化につながる.
- Cope型の再配置とイライドの中間物質を含む提案されたメカニズムは,DFT計算によってサポートされています.
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