インドールベースのオニウムイリドの再配置における触媒制御地域分散
Vaishnavi N Nair1, Volga Kojasoy2, Croix J Laconsay2
1Department of Biochemistry, The University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, United States.
Journal of the American Chemical Society
|June 14, 2021
まとめ
ロジウムと銅の触媒を用いた インドル再配置の新方法を開発しました この突破により 複雑なインドルアルカロイドの合成が可能になり 新しい合成経路が提供されます
科学分野:
- 有機化学
- キャタリシス
- 合成方法論
背景:
- インドール・スキャフォールは天然製品や医薬品に多く含まれています.
- 地域選択性を制御することは,重要な合成課題です.
研究 の 目的:
- インドル由来オニウムイリドの触媒制御された地域分散的再配列を開発する.
- 実験的および計算的方法を使用してこれらの再配置のメカニズム的経路を調査する.
- 自然製品合成におけるメソドロジーの有用性を実証する.
主な方法:
- 置換されたインドルからオキシオニウムイリドの局所生成.
- ロジウム ([2,3]リアレンジメント) と銅 ([1,2]リアレンジメント) を使用した触媒.
- 反応メカニズムを解明するための密度関数理論 (DFT) の計算.
主要な成果:
- 選択的な[2,3]-および[1,2]-再配置は,使用した触媒に基づいて達成されました.
- 機械学的研究により,ロジウム触媒の金属フリーイライドと,銅触媒の金属調整イオンペアという異なる経路が明らかになった.
- この方法は,インドルアルカロイド (±) - ソラゾロンBの最初の完全合成に成功しました.
- (±) - ソラゾロンBのステレオ化学は,合成に基づいて再割り当てされました.
- 再編成された製品は 有価な合成中間製品に変換された.
結論:
- インドールイリドの汎用性のある触媒制御された地域分散型再配置戦略を開発した.
- 異なる経路のメカニズムを明らかにした.
- 複雑なインドルアルカロイドと関連化合物の合成のための強力なツールを提供した.
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