弱調整ヒドロキシル群によるエナレンの高度にダイアステロセレクティブなパラジアム触媒による酸化カルボサイクリング
Daniels Posevins1, Youai Qiu1, Jan-E Bäckvall1
1Department of Organic Chemistry, Arrhenius Laboratory , Stockholm University , SE-106 91 Stockholm , Sweden.
Journal of the American Chemical Society
|February 10, 2018
まとめ
新しいパラジウム触媒反応により,エナレンから機能化されたサイクロヘクセンール誘導体の合成が可能である. この方法は,反応経路を指示するヒドロキシル基を用いて,ステレオ化学に対する高い制御を提供します.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- パラジウム触媒反応はC−C結合形成に不可欠である.
- 複雑な分子合成のためのダイアステレオ選択的方法の開発は,依然として課題です.
研究 の 目的:
- エナレンの新型酸化カルボサイクライゼーション-ボリレーションを開発する.
- サイクロヘクセノール誘導体の形成において高いダイアステロ選択性を達成する.
主な方法:
- 酸化カルボサイクリング-ボリレーションのためのパラジウム触媒を用いる.
- 反応を誘導する弱調整ヒドロキシル基を用いる.
- リガンド交換とオレフィン調整を含むメカニズムを調査する.
主要な成果:
- 制御された1,3-相対ステレオ化学 (d.r. > 50:1) でした.
- 他の酸素を含むグループ (ケトン,アルコキシド,アセテート) も炭水化物を促進することが示された.
- 反応の成功のために,近接酸素を含む機能の必要性を確立した.
結論:
- エナレンの機能化のための高度にダイアステロセレクティブなパラジウム触媒反応が開発された.
- ヒドロキシルグループは,顔選択的調整を通じてステレオ化学を指揮する上で重要な役割を果たします.
- この方法論は複雑なサイクル構造を構築するための強力なツールを提供します.
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