形状的に安定したC ((sp2) -C ((sp3) アトロピソーマの有機触媒エナチオセレクティブ構造
Giulio Bertuzzi1, Vasco Corti1, Joseph A Izzo1
1Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|January 6, 2022
まとめ
研究者らは,安定した立体軸を持つ分子であるキラルC ((sp2) - C ((sp3) アトロピソーマを合成するための新しい方法を開発した. この有機触媒的アプローチは高いステレオ選択性を達成し,これらの複雑な化合物を生成するための一般的なプロトコルを提供します.
科学分野:
- 有機化学
- ステレオ化学
- 非対称合成
背景:
- ノンビアリルアトロピゾーマーには,少なくとも1つのノンアレン基を持つステレオゲンな軸がある.
- 形状的に安定したC ((sp2) -C ((sp3)) ステレオジェニック軸は天然製品に見られるが,その合成は十分に研究されていない.
研究 の 目的:
- 新種のキラルC ((sp2) -C ((sp3) アトロピソーマのエナンチオセレクティブ合成の開発.
- 多様な分子モチーフを持つこれらの化合物を作るための広範で一般的なプロトコルを確立する.
主な方法:
- 器官触媒的非対称的な方法が採用されました.
- 密度関数理論 (DFT) の計算が用いられた.
- 形状の安定性と反応メカニズムを分析するために実験的調査が行われました.
主要な成果:
- 高いステレオ選択性 (最大99% ee) を有するキラルC ((sp2) -C ((sp3))) アトロピソーマの新種が合成された.
- C (sp2) - C (sp3) ステレオジェニック軸は,著しい構造安定性を示した (t1/2>25°Cで1000年).
- ステレオジェニック要素に対する運動制御が観察され,Curtin-Hammettシナリオを支持する証拠が示された.
結論:
- 開発された有機触媒法は,新しいC ((sp2) -C ((sp3) アトロピソマーへの一般的で高度にステレオ選択的な経路を提供します.
- この研究は,この希少なステレオジェニック元素を制御する形状の安定性と運動制御に関する洞察を提供します.
- 中心から軸性キラリティ変換の証拠が得られ,立体化学変換の理解が進んだ.
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