トレン覆いヘクサフィリン亜鉛複合体:分子認識,モビウス芳香性,キラリティの相互作用
Hervé Ruffin1, Gildas Nyame Mendendy Boussambe1, Thierry Roisnel1
1Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de Rennes 1 , 263 avenue du Général Leclerc, 35042 Rennes cedex, France.
Journal of the American Chemical Society
|September 14, 2017
まとめ
研究者らは高度な分子認識のための新しいトレインカバーヘクサフィリンを開発しました. これらのモビウス芳香化合物は,選択的金属結合とキラル誘導を示し,センシングと触媒における新しい応用を可能にします.
科学分野:
- 超分子化学
- 有機化学
- 材料科学
背景:
- ヘクサフィリン・スキャフォードは,ポルフィリンを超えてユニークなトポロジー,芳香性,金属の協調性特性を提供しています.
- ヘクサフィリンを用いた分子認識研究は,洗練された宿主を作るための汎用的な合成戦略がないため,限られています.
研究 の 目的:
- ヘクサフィリンベースの複雑な分子宿主を作るための一般的な合成戦略を開発する.
- 新しいヘクサフィリン誘導体の 分子認識能力を調査する.
主な方法:
- メソ−−アミノフェニル−トリス置換プラットフォームの合成後の改変で,トリス−−アミノエチル−アミンのような三脚単位でヘクサフィリン枠を封じます.
- メタリングとリガンド結合時の形状の変化を含む,結果として発生したトレン・キャップヘクサフィリンの特徴.
- キラルアミノリガンドを用いたキラル誘導とキラル光学特性の評価.
主要な成果:
- トレン・キャプテッド・ヘクサフィリンは3段階で合成され,28π結合系を示した.
- Zn ((II) メタリングは平面から曲がった形状の変化を誘導し, π オーバーラップを保ちながら,Hückel 反芳香から Möbius 芳香に変換した.
- トレンユニットプロトネーションによるアロステリックチューニングにより,アセタトとアミノリガンドの選択的および協力的結合が観察された.
- キラルアミノリガンドで高いキラル誘導 (最大77%のダイアステロエーマー過剰) が達成され,強力な円形二重化信号が生じた.
結論:
- 開発された合成アプローチは,分子認識のための洗練されたヘクサフィリンホストへのアクセスを提供します.
- トレン覆いヘクサフィリンは,調節可能な電子特性と選択的なゲスト結合を示し,メタロ酵素の活性部位を模倣する.
- これらのモビウス芳香化合物は,キラルセンシングと触媒の応用に重要な可能性を示しています.
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