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Ni (III) を媒介する二重C-H活性化による芳香性シアノアルキル化

Wen Zhou¹, Shuai Zheng¹, Jason W Schultz¹

¹Department of Chemistry, Washington University , St. Louis, Missouri 63130-4899, United States.

Journal of the American Chemical Society

|April 28, 2016

まとめ

この研究は,ニトリルを用いた芳香的シアノアルキル化のための新しいニッケル触媒反応を導入する. 高値ニッケル (III) センターでC-H結合活性化を実現し,複雑なニトリルの効率的な合成を可能にします.

科学分野:

有機化学
カタリシス
有機金属化学

背景:

C−H結合の活性化は有機合成における重要な変換である.
ニッケル触媒は,新しい合成方法論を開発するための汎用的なプラットフォームを提供します.
高価金属種は,低酸化状態と比較してユニークな反応性を示すことができます.

研究の目的:

原子とステップ経済的なアロマティックシアノアルキル化反応を開発する.
ニッケル (III) 触媒によるC−H結合の活性化を探求する.
反応の地域選択性と基質の範囲を調査する.

主な方法:

シアノアルキル化のための構成要素としてニトリルを使用する.
ニッケル (III) 触媒を用いてCsp (−2) -HとCsp (−3) -H結合を活性化する.
反応産物と中間産物の特徴

主要な成果:

原子とステップ経済的なアロマティックシアノアルキル化が達成された.
様々なニトリルによる地域選択的α-シアノアルキル化が実証されている.
二次性や三次性ニトリルを効率的に生成する.
Ni (III) センターでのC-H結合活性化の最初の例を報告した.

結論:

開発されたNi (III) 触媒反応は,ニトリル合成のための新しい経路を提供します.
Ni (III) センターでのC-H活性化は,明確な反応性と選択性を提供します.
これらの発見は,高価ニッケル種を用いた触媒C−H活性化反応の設計のための指針となる.

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