水酸化ピネル誘導体のフェンコン型フレームワークへの再配置:動的に制御された選択性の計算的証拠

Marcus Blümel¹, Shota Nagasawa¹, Katherine Blackford¹

¹Department of Chemistry , University of California , Berkeley , California 94720 , United States.

Journal of the American Chemical Society

|July 4, 2018

まとめ

新しい酸触媒反応は,水酸化ピネン誘導体から複雑な三環フェンコン型構造を効率的に生成します. この方法は,独特の移行後の状態のバイフォケーションメカニズムによって制御される高収量と選択性を提供します.

科学分野:

有機化学
反応メカニズム
ステレオ選択合成

背景:

ピネン系は貴重な天然製品である.
複雑な骨組みへの効率的な合成経路の開発は極めて重要です
反応メカニズムの理解が合成戦略を導きます

研究の目的:

三回転フェンコン型構造を合成するための新しいカスケード反応を開発する.
反応のメカニズムと選択性を調査する.
ステレオ選択性の制御における量子化学の洞察の役割を探求する.

主な方法:

酸触媒によるプリンス/セミピナコール再配列カスケード反応
起料としてヒドロキシル化ピネン誘導体を利用した.
量子化学分析を使って移行状態を研究した.

主要な成果:

フェンコンの型で非常に高い収穫量とダイアステレオ選択性を得ています.
移行状態の周辺に非常に平らな潜在エネルギー表面を特定した.
ボルニル骨格よりもフェンコンを好む移行後の状態のバイフォーケーション (PTSB) による動的制御が実証された.

結論:

新しく効率的な合成経路が確立されています.
量子化学分析は,選択性の重要なメカニズム的理解を提供します.
PTSBメカニズムは,複雑な反応におけるステレオ化学的結果の制御のための新しいパラダイムを提供します.

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