プロパルギルおよびアルリル基の触媒性エナントオセレクティブ1,6結合添加
Fanke Meng1, Xiben Li1, Sebastian Torker1
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Nature
|August 2, 2016
まとめ
この研究は,プロパルギルとアルリル基を組み込んだ,ダイノアートへのエナチオセレクティブの1,6-結合添加剤のための新しいオーガノコッパー触媒を導入する. 薬剤を含む複雑な分子のための 新しい合成経路を可能にします
科学分野:
- 有機化学
- カタリシス
- 薬剤化学
背景:
- 有機合成において,触媒エナチオセレクティブ結合添加は極めて重要です.
- エナチオセレクティブの1,6-結合添加物は,特にプロパルギルやアルリルなどの機能化群は,まれである.
- 1,6-添加のための既存の方法は,範囲と基板の互換性において制限されています.
研究 の 目的:
- アサイクリックダイノアートへの1,6結合添加のための触媒的エナンチオセレクティブ法を開発する.
- プロパルギルと2ボリル置換アルリル群をダイノ酸受容体に組み込む.
- 開発された触媒システムのメカニズムと選択性を解明する.
主な方法:
- 結合結合反応のための器官銅の触媒の開発.
- 商業的に利用可能なアレンイル-ボロン化合物または単体置換アレンを核愛体として利用する.
- 反応機構と選択性を理解するために,密度関数理論 (DFT) の計算を使用する.
主要な成果:
- オーガノコッパー触媒は,プロパルギルと2-ボリル置換アルリル基の1,6結合添加をダイノアートに効果的に促進する.
- 高い収量 (83%まで),二重選択性 (> 98: 2),およびエナチオ選択性 (99: 1) が達成されました.
- 機理学的な研究は,触媒構造に基づくサイトとエナチオ選択性の起源を明らかにした.
結論:
- 新しく利用可能な有機銅触媒は,高度に選択的なエナチオセレクティブの1,6結合添加を可能にします.
- この方法により,有価な機能群をアサイクリック・ダイノアートに導入することができる.
- 開発されたアプローチは,抗HIV剤 (-) - エクセチンのエナチオセレクティブ合成に成功しました.
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