Csp3-Csp3 定型銅 (III) 複合体からの結合形成還元除去
Matthew Paeth1, Sam B Tyndall1, Liang-Yu Chen2
1Department of Chemistry and Biochemistry , Miami University , Oxford , Ohio 45056 , United States.
Journal of the American Chemical Society
|January 26, 2019
まとめ
研究者は炭素−炭素結合形成のための安定した有機銅 (III) 複合体を合成した. これらの複合体は,銅触媒反応を進めて,還元性除去によってアルキル-CF3製品を効率的に生成する.
科学分野:
- 有機金属化学
- キャタリシス
- 合成化学
背景:
- 銅が触媒となる反応は有機合成において不可欠である.
- 器官銅 (III) 複合体は重要な中間物質ですが,めったに分離されません.
- これらの種からCsp3-Csp3結合の形成は特に困難です.
研究 の 目的:
- 安定した有機銅 (III) 複合体を合成するための一般的な方法を開発する.
- Csp3-CF3結合形成のためのこれらの複合体の還元性除去を調査する.
- この還元性排除プロセスのメカニズムを解明する.
主な方法:
- [アルキル-CuIII-CF3]-複合体の合成
- NMRスペクトロスコーピー,質量スペクトロメトリー,X線結晶学を用いた構造的特徴づけ.
- 運動研究と密度関数理論 (DFT) の計算.
主要な成果:
- よく定義された[アルキル-CuIII-CF3]-複合体の一連の合成と特徴は成功しました.
- これらの複合体は,高温で第1次還元性除去を行い,アルキル-CF3製品を最大91%の収量で生成します.
- キネティックとDFTの研究は,Csp3-CF3結合形成のための協調された移行状態を,20 kcal/molのバリアで明らかにした.
結論:
- 安定した有機銅 (III) 複合体は合成され,Csp3-CF3結合形成の有効な前駆体として機能する.
- 還元性除去は協調したメカニズムによって行われ,銅触媒によるクロスカップリング反応に関する貴重な洞察を提供します.
- この研究は,トリフローロメチル化化合物を合成するための新しい経路を提供します.
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