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機能化と多様化の戦略に従って,アリルC-Hボンドのエナチオセレクティブ機能化

Ankit Sharma¹, John F Hartwig

¹Department of Chemistry, University of California , Berkeley, California 94720, United States.

Journal of the American Chemical Society

|October 26, 2013

まとめ

この研究は,アルケンのアリルC-H結合のエナチオ選択的機能化のための新しい方法を導入しています. このプロセスは,生物学的活性分子に関連するものを含め,さまざまなキラル製品に対して,高い収穫量と優れたエナチオセレクティブ性を達成します.

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:

C-H結合の機能化は,合成化学の重要な分野である.
複雑な分子のエナチオセレクティブ合成は,依然として大きな課題です.
アリル型機能化は,多様な分子構造への経路を提供します.

研究の目的:

終端アルケンのアルリルC-H結合の機能化のための新しいエナンチオセレクティブ・メソッドの開発.
高い選択性と産出率を持つキラル分子の合成を可能にするために.
生物学的に重要な化合物を合成する開発方法の有用性を実証する.

主な方法:

パラジウム触媒によるC-H酸化を伴う1ポット配列で,線形アルリルベンゾアートを形成する.
その後のイリジウム触媒によるアリル基置換により,様々な核好性物質が形成される.
高い線形選択性のための酸のないアリル酸化の開発.

主要な成果:

末端アルケンのアリルC-H結合のエナチオ選択的機能化が成功しました.
新しいC-N,C-O,C-S,またはC-C結合を持つ多様なキラル産物の形成.
枝分かれから線形への高い選択性と優れたエナチオ選択性 (最大97% ee) を達成した.
分離された酸化と機能化のステップによる広範な範囲が実証されています.
繰り返し配列は,触媒制御された (1,n) 機能化を可能にします.

結論:

開発された方法は,エナチオセレクティブのアリル機能化のための強力なツールを提供します.
この戦略は,複雑なキラル分子を高効率で合成することを可能にします.
このアプローチは,生物学的に活性な分子の合成に適用できます.

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