鉄触媒によるC-C結合形成は,1,5-水素移転によるC-H結合活性化によるアリファ酸アミンのアルファ位置でのC-C結合形成である
Naohiko Yoshikai1, Adam Mieczkowski, Arimasa Matsumoto
1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033.
Journal of the American Chemical Society
|April 6, 2010
まとめ
鉄のカタリシスにより,C-Hの機能化は,ラジカルのような中間体によって可能になる. この研究は,sp(3) C−H結合の効率的なアリレーション,アルケニル化,アルキル化のための新しい有機鉄媒介反応を詳細に説明しています.
科学分野:
- 有機金属化学 有機金属化学
- オーガニック・シンセシス オーガニック・シンセシス
- カタリシス カタリシス カタリシス
背景:
- 炭素-炭素結合の形成は,有機合成において不可欠である.
- オルガノアイロンの種は,激素のような特徴を持つ反応を媒介することができます.
- sp(3) C-H 債券の直接機能化は,合成的な課題であり続けています.
研究 の 目的:
- C-H機能化のための新しい鉄触媒法を開発する.
- オーガノアイロン媒介のアリレーション,アルケニレーション,アルキレーションの範囲を調査する.
- ラジカル転位を伴うメカニズムを解明する.
主な方法:
- N-(2-イオドフェニルメチル) ディアルキイラミンの反応とグリナードまたはディオルガノジンシンの反応剤.
- 鉄 (III) アセチラケトネート (Fe ((acac) ((3)) の触媒用量を使用した.
- 同位体ラベリング実験を含むメカニズム調査.
主要な成果:
- アリレーション,アルケニル化,またはアルキル化による製品の良好から優れた収量を達成します.
- アミン群の隣接する sp(3) C-H 結合の機能化が実証された.
- 証拠は,ヨウ素除去によって開始された急性転位を含むメカニズムを示唆しています.
結論:
- 効率的な鉄触媒C-H機能化戦略を開発しました.
- この方法論は,多様なC−C結合形成を可能にする.
- 反応は,オルガノアイロンの種によって媒介される根幹転位経路を経由して進みます.
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