N-Hydroxyphthalimideを用いた分子間ラジカル媒介型アンチマルコフニコフアルケンの水酸化
Samuel W Lardy1, Valerie A Schmidt1
1Department of Chemistry and Biochemistry , University of California, San Diego , La Jolla , California 92093 , United States.
Journal of the American Chemical Society
|September 8, 2018
まとめ
新しい方法により,トリエチルフォスフィートとN-ヒドロキシフタリミドを用いた様々なアルケンのアンチマルコフニコフ製水酸化が可能になる. この反応は,N-アルキルフタリミド中間体を通って,一次アミンへの多用途の経路を提供する.
科学分野:
- 有機化学
- 合成方法論
背景:
- 窒素を含む化合物の合成には,水素化反応が不可欠である.
- 効率的で選択的な分子間ヒドロアミネーションの方法の開発は依然として課題です.
研究 の 目的:
- アルケンの新しい分子間抗マルコフニコフ水素化を開発する.
- 主要なアミンを入手するための多用途な方法を確立する
主な方法:
- トライエチルフォスフィートとN-ヒドロキシフタリミドを主要反応剤として使用した.
- ビニルエーテル,シラン,硫化物,活性化されていないアルケーンを含む様々なアルケーンとの反応範囲を調査した.
- 反応経路を明らかにするために機械的な探査機を使用した.
主要な成果:
- 幅広いアルケンの分子間抗マルコフニコフ水素化に成功しました.
- アルケンの基板内の多様な機能群の耐性を示した.
- N-アルキルフタリミドの原始アミンへの容易な変換を示した.
- フタリミジルラジカルを含む,フォスフィット誘発の急性脱酸素化メカニズムを特定した.
結論:
- 抗マルコフニコフ水素化のための頑丈で多用途な方法を開発しました.
- この方法論は,原始アミンの合成のための貴重な経路を提供します.
- メカニズム的な理解は,リン酸媒介の過激なプロセスへの洞察を提供します.
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