TEMPO-N3複合体によるアルケンの電気化学的アジド酸化
Juno C Siu1, Gregory S Sauer1, Ambarneil Saha1
1Department of Chemistry and Chemical Biology , Cornell University , Ithaca , New York 14853 , United States.
Journal of the American Chemical Society
|August 31, 2018
まとめ
新しい電気化学的方法により,アルケーンから近隣のC-OとC-N化合物を効率的に合成します. このTEMPO媒介の経路は,合成化学の応用を拡大する新しいアジジル基機構を含んでいます.
科学分野:
- 有機化学
- 電気化学
- 合成方法論
背景:
- TEMPO (2,3-ジメチル-2,3-ディニトロブタン) 基質化学は有機合成において極めて重要です.
- 既存のTEMPO媒介反応は,しばしば異なるメカニズムの経路を伴う.
- アルケンの軽度かつ効率的な機能低下プロトコルの開発は,依然として活発な研究分野である.
研究 の 目的:
- アルケンの機能破壊のための 軽く効率的な電気化学プロトコルを確立する.
- 反応メカニズム,特にTEMPOとアジドの役割を解明する.
- 合成された製品の有用性を探求する.
主な方法:
- 単純なアルケーンとアジドの源を用いた電気化学合成.
- DFTの計算とスペクトル学的特徴を含む詳細なメカニズム調査.
- 運動研究と運動同位体効果測定
主要な成果:
- 新しい電気化学プロトコルは C-OとC-Nの二機能化化合物へのアクセスを提供します.
- TEMPO-N3電荷移転複合体とアジジル基の形成を伴う明確な反応機構が発見されました.
- 速度を決定するステップは,TEMPO-N3の可逆的な解離と,アルケンの後の急性添加を含みます.
結論:
- この研究は,アルケンの機能不全のための新しい効率的な電気化学的経路を示しています.
- アジジル基を含むTEMPO媒介反応の新しいメカニズムが解明されました.
- この発見により,アミノキシルラジカル化学の合成応用が広がった.
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