保護されたアミンを生成するための光誘導,銅触媒分解性C-Nカップリング:カーティウス再配列の代替方法

Wei Zhao¹, Ryan P Wurz², Jonas C Peters¹

¹Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.

Journal of the American Chemical Society

|August 26, 2017

まとめ

研究者らは銅の触媒と青いLED光を用いたカーティウス再配置のより安全な代替手段を開発しましたこの方法は,危険なアジドを避け,炭酸誘導体を温和な条件下で保護されたアミンに効率的に変換します.

科学分野:

有機化学
写真化学
カタリシス

背景:

カーティウスの再配列は,炭酸から保護されたアミンを合成するための重要な方法である.
しかし,その適用は,アジドの取り扱いに伴う安全上の懸念によって制限されています.
より安全で穏やかな代替品の開発は幅広い合成用途に不可欠です

研究の目的:

保護されたアミンを合成するための新しく安全で穏やかな方法を確立する.
アジド依存のカーティウス再配列の代替品を提供するためです.
銅触媒による脱炭酸化C-N結合の形成を調査する.

主な方法:

銅の触媒と青いLEDの照射を用いた
アリファートカルボキシル酸のN-hydroxyphthalimide (NHPI) エステルを使用しています.
反応の範囲を調査し,コントロールとメカニズム研究を行った.

主要な成果:

NHPIエステルのデカーボキシル結合が,穏やかな条件下で保護されたアミンを形成する.
アルコール,エポキシド,および硫化物を含む幅広い機能群への耐性が実証されています.
機械学的研究では,コッパーが関与する光還元触媒サイクルは,外部の根の結合を示唆しています.

結論:

カーティウスの再配置の代替として,安全で効率的な銅触媒フォトレドックス法を開発した.
新しいプロトコルは,軽度の反応条件と優れた機能群の互換性を提供します.
このアプローチは,有機化学におけるアミンの合成のための貴重なツールを提供します.

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