モノヒドロキシキュルビット[n]ウリルの総合合成 (n = 5,6,7,8):高純度および高変換
Mehmet M Ayhan1,2, Hakim Karoui1, Micaël Hardy1
1†Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, 13397 Marseille, France.
Journal of the American Chemical Society
|July 22, 2015
まとめ
新しい光化学的方法により,水素過酸化物と紫外線を用いて,キュルビチューリル (CB[n]) の単一アルコール機能化が可能です. このスケーラブルな技術は,反応機構の洞察を提供し,新しいCB[n]誘導体を生成します.
科学分野:
- 有機化学
- 写真化学
- 超分子化学
背景:
- キュルビチューリル (CB[n]) は,限られた合成改変オプションを持つマクロサイクル宿主です.
- CB[n]の機能化のための効率的な方法の開発は,そのアプリケーションの拡大に不可欠です.
研究 の 目的:
- キュキュルビチューリルの直接的な単一機能化のための新しい光化学的方法を開発する.
- 機能化プロセスの反応メカニズムとスケールアップの可能性を調査する.
主な方法:
- 水素過酸化物と紫外線を用いた光化学反応
- スピン・トラッピングと質量スペクトロメトリー (MS) を用いて基質の特徴を決定する.
- 同位体で標識された水の実験 ((18) O).
- ボンド分離エネルギー (BDE) の密度関数理論 (DFT) 計算
主要な成果:
- CB [5],CB [6],CB [7],およびCB [8]の直接アルコール機能化のための95%から100%の変換を達成しました.
- CB[6]とCB[7]に対する反応を1gにスケールアップした.
- 反応メカニズムで識別された急性およびイオン中間物質.
- DFTの計算は,赤道的なC-H債券とCBとの挑戦の好ましい反応性を説明した[8].
- CB[5]-(OH) 1と最初のCB[8]誘導体,CB[8]-(OH) 1が得られた.
結論:
- 開発された光化学的方法は,単一機能のキュルビチューリルを合成するための簡単で効率的な経路を提供します.
- この研究は,CB[n]機能化に関与する激素とイオン経路に関する機械的洞察を提供します.
- この研究は,機能化されたキュキュルビチューリル,特にCBの合成アクセシビリティを拡大する[8].
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