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非活性化オレフィンとアルキルハリドの銅触媒型分子間反応
Chunlin Tang1, Ran Zhang1, Bo Zhu1
1Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry , Northeast Normal University , Changchun 130024 , China.
Journal of the American Chemical Society
|November 14, 2018
まとめ
研究者は,未活性化オレフィンとアルキルハリドの結合により,アルキルオレフィン化のための新しい銅促進反応を開発した. この方法は,高い選択性と幅広い基板範囲を提供し,有価なアルキルオレフィン製品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
背景:
- 活性化されていない基質の分子間アルキラティブオレフィネーションは依然として困難です.
- C−C結合形成のための選択的方法の開発は,有機合成において極めて重要です.
研究 の 目的:
- 活性化されていないオレフィンとアルキルハリドの新しい分子間アルキラティブオレフィネーションを確立する.
- アルキルハリドとアルケンの結合において高い地域とステレオ選択性を達成する.
主な方法:
- 銅が促進したヘック型反応.
- 基板活性化のための指向グループ戦略を利用した.
- 反応メカニズムを解明するために,密度関数理論 (DFT) の計算を使用した.
主要な成果:
- 活性化されていないオレフィンとアルキルハリドの最初の分子間アルキルオレフィン化が成功しました.
- クープリングされたアルキルオレフィン産物の形成において優れた地域とステレオ選択性を示した.
- 主要,二次,三次アルキルブロミドおよび様々なアルケンを容認する幅広い基板の範囲を示した.
結論:
- 開発された銅促進反応は,アルキルオレフィン製品への効率的な経路を提供します.
- Cu (III) 周期的移行状態を介して,ジメチル硫化物による協調したH-Br除去が提案されています.
- この方法論は,すぐに利用可能な出発材料を使用して,C-C結合形成のためのツールキットを拡張します.
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