1,1-非置換サイクロペンタンのC ((sp3) -C ((sp3) とC ((sp3) -H結合の活性化
Chisato Mukai1, Yuu Ohta, Yuki Oura
1Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. mukai@p.kanazawa-u.ac.jp
Journal of the American Chemical Society
|November 14, 2012
まとめ
この研究は,前例のないC ((sp ((3)) -C ((sp ((3)) の結合裂けを,ロジウム ((I)) 触媒を用いた非活性化されたサイクロペンタンで実証している. 新しいバイサイクリックおよびスパイロサイクリック化合物は,新しいサイクル添加反応によって合成されました.
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 (((sp ((3)) -C (((sp ((3)) の結合割れは,特に活性化されていない循環アルカンでは困難です.
- ロジウム ((I) 触媒は,新しい結合活性化と変換の可能性を秘めています.
研究 の 目的:
- 未活性化されたサイクロペンタンの前例のないC(sp(3)) -C(sp(3)) 結合割れを実現する.
- 複雑な多循環構造への新しい合成経路を開発する.
主な方法:
- ロジウム ((I) 触媒によるアルキネス・アルニル・サイクロペンタン・サイクロアディション.
- ロダビサイクロ[4.3.0]ノナ-1,6-ディエンの中間物質のインサイト生成.
- [7+2] β-C 除去によるサイクル添加.
- サイトセレクティブのCγ-H結合活性化は,Rh ((I)) 触媒を変化させることで行われる.
主要な成果:
- 活性化されていないサイクロペンタンのC ((sp (((3)) -C ((sp (((3))) 結合の切断が成功しました.
- バイサイクロ[7.4.0]トリデカトリエン誘導体の形成は,良好な収穫量で.
- サイト選択Cγ-H活性化による新型スピロ[2.4]ヘプタン骨格の合成.
結論:
- ロジウム ((I) 触媒は,サイクロペンタンの前例のないC ((sp ((3)) -C ((sp ((3)) 結合割れを可能にします.
- ビサイクロ[7.4.0]トリデカトリエンとスピロ[2.4]ヘプタン骨格のための新しい合成戦略が確立されています.
- 触媒の改変により,サイト選択的なC-H活性化が可能になり,合成の有用性を拡大します.
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