P (III) /P (V) - アリルボロン酸とエステルの触媒メチラミネーション:メチラミンサロゲートとしてのニトロメタンとの還元性C-N結合
Gen Li1, Ziyang Qin1, Alexander T Radosevich1
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|September 4, 2020
まとめ
研究者は,ニトロメタンの直接的なN-アリレーションのための新しい有機リン触媒方法を開発しました. この効率的なC-N結合はメチラミノ置換の芳香物質を作り,同位体として標識されたN-メチラニリンの合成を可能にします.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- 直接のN-アリレーションは有機合成における重要な変換である.
- 既存の方法はしばしば厳しい条件や複雑な触媒を必要とする.
- ニトロメタンは安価で簡単に手に入るC1の構成要素です.
研究 の 目的:
- ニトロメタンの新種の有機リン触媒による直接的還元性N-アリレーションを開発する.
- 温和で効率的なC-N結合形成方法を確立する.
- 同位体で標識されたN-メチラニリンを合成するためのこの方法の有用性を実証する.
主な方法:
- アリルボロン酸誘導体を用いた有機リン触媒による還元性C-N結合
- 小環有機リン触媒 (1,2,3,4,4-ヘクサメチルフォスフェタンP酸化物) を使用する.
- 軽い末端減量剤 (ヒドロシラン) を使用する.
主要な成果:
- アリルボロン酸とエステルによるニトロメタンの直接的還元性N-アリレーションの成功
- メチラミノ基を (ヘテロ) アロマティック基板に選択的に設置する.
- 様々な同位体で標識されたN-メチラニリン (CD3NO2,CH315NO2,13CH3NO2) を合成するための統一されたアプローチを示した.
結論:
- ニトロメタンは直接メチラミノ群の設置のための多用途の前駆体として機能する.
- 開発された方法は,N-メチラニリン誘導体への直接的かつ効率的な経路を提供します.
- この方法論は,研究のために価値ある同位体でラベル付けされた化合物の合成を容易にする.
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