タンデムC/N-ニトロアーネスの機能低下:リング拡張/収縮配列による還元性アミネーションおよび無効化
Gen Li1, Marissa N Lavagnino1, Siraj Z Ali1
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|December 23, 2022
まとめ
新しい合成法で,ナイトロアレンを価値あるオルトアミネート製品に変換します. この有機リン触媒によるプロセスは,アリルナイトレンを生成し,アゼピンと,最終的にアニリドとベンジミダゾールを脱オロマ化させます.
科学分野:
- 有機化学
- 合成方法論
- カタリシス
背景:
- ニトロアレン変換は有機合成において極めて重要です.
- オルト機能化のための効率的な方法の開発は,依然として課題です.
- 複雑な窒素を含むヘテロサイクルにアクセスするには,革新的な戦略が必要です.
研究 の 目的:
- ニトロアレンを還元的に変換するための新しい合成方法について報告する.
- オーソアミネーションと アロマティックシステムの無効化
- 2アミノアニリドとベンジミダゾール誘導体を合成する
主な方法:
- オルガノフォスファース触媒と軽度な還元剤を用いた窒素酸塩の徹底的な脱酸素化.
- アリルナイトレンの生成と捕獲
- 環の膨張により,2-アミノ-3H-アゼピンが形成される.
- 6π電循環とC-H機能化に続くアシル電化処理.
主要な成果:
- 開発された方法は,ニトロアレンをオルトアミネ化および無効化製品にうまく変換します.
- アリルナイトレンは生成され,その後アミンヌクレオフィールによって閉じ込められる.
- 2アミノ3Hアゼピンは重要な中間物質として形成される.
- このプロセスは,C-H機能化により,2-アミノアニリドおよびベンジミダゾール製品を生成する.
結論:
- オーソ機能化された芳香化合物へのアクセスのための汎用的な合成経路が確立されています.
- この方法は,2-アミノアニリドとベンジミダゾールの有価な基板への新しい経路を提供します.
- この研究は,有機化学におけるナイトロアレンの合成的有用性を拡大する.
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