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軽度のパラジウム触媒によるニトリルの選択的モノアリレーション

Lingyun Wu¹, John F Hartwig

¹Department of Chemistry, Yale University, New Haven, Connecticut 06510, USA.

Journal of the American Chemical Society

|November 10, 2005

まとめ

新しいパラジウム触媒法により,より穏やかな条件下で,ナトリルの効率的なアリレーションが可能になります. これらの反応により,薬剤や合成において重要な価値あるベンジルニトリルが生成され,アルファシリルニトリルや亜鉛反応剤を用いる.

科学分野:

有機化学オーガニック・ケミストリー
カタリシスカタリシスカタリシス
合成方法論合成方法論

背景:

パラジウムによって触媒化されたクロスカップリング反応は,有機合成において極めて重要です.
伝統的なニトリルアリレーション方法は,しばしば厳しい基本条件を必要とし,機能群の互換性を制限します.

研究の目的:

より穏やかな,より基本的な条件下で,ニトリルアリレーションのための新しいパラジウム触媒プロセスを開発する.
効率的な触媒経路を通じてベンジルニトリルの合成有用性を拡大する.

主な方法:

ニトリルに対する2つの異なるパラジウム触媒のアリレーション戦略を開発した.
アルファシリルニトリルとZnF2を用いて,プライマリニトリルの選択的モノアリレーションを行っています.
亜鉛シアノアルキル反応剤を使用し,二次ニトリルのアリレーションを行います.

主要な成果:

アセトニトリルとプライマリニトリルの選択的単離化が達成され,機能群の耐性が広く認められる.
塩基耐性条件下で二次性ニトリルのアリレーションで高い収量を得ました.
心血管薬であるヴェラパミルの合成を実証し,これらの方法の実用的な応用を示した.

結論:

開発された方法は,多様なベンジル酸ナトリルに効率的で汎用的な触媒経路を提供します.
これらの手順は,様々な塩基敏感機能群と互換性があり,合成の範囲を拡大します.
新しい結合反応は,生物学的に重要な化合物や合成中間物質にアクセスするための貴重なツールを提供します.

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