非対称C-C活性化による (-) - サイクロクラビンと (-) - 5 - エピサイクロクラビンの簡潔な合成
Lin Deng1, Mengqing Chen1,2, Guangbin Dong1
1Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States.
Journal of the American Chemical Society
|July 7, 2018
まとめ
この研究は,C-C活性化による (-) - サイクロクラビンの効率的な合成を示しています. この新しいRh触媒による"カット・アンド・シュー"方法は,わずか10段階で高いエナチオ選択性を達成します.
科学分野:
- 有機化学
- 合成化学
- キャタリシス
背景:
- 自然製品の合成は 薬の発見と生物学的過程の理解に不可欠です
- 複雑な分子のための効率的でエナチオセレクティブな合成経路の開発は,有機化学における重要な課題です.
- 複雑な分子構造を構築するための強力なツールを提供します.
研究 の 目的:
- C-C活性化戦略の合成的有用性を実証する.
- (-) - サイクロクラビンと (-) - 5 - エピサイクロクラビンのエナンチオセレクティブ・トータル合成を達成する.
- 複雑な天然製品の合成のための効率的で広く適用可能な触媒システムを開発する.
主な方法:
- ベンゾサイクロブテノンとオレフィン間の非対称なRh触媒"カット&シュー"変換.
- ベンゾサイクロブテノンの構築のためのパラジアム触媒のタンデムC-N結合/アリルアルキル化.
- テトラ置換されたサイクロプロパン形成のためのダイアステロ選択的サイクロプロパネーション.
主要な成果:
- (-) サイクロクラビンと (-) 5エピサイクロクラビンの合成は10段階で行われ,総生産量は30%に達した.
- 高度にエナチオセレクティブなRh触媒によるカルボアシレーションにより,インドリン融合型三環核が形成された.
- カット・アンド・シュー反応の触媒条件の改善により,94~99%のエナティオメール過量 (すなわち ) でした.
結論:
- 開発されたC-C活性化戦略は,複雑な天然製品を合成するのに非常に効率的です.
- この方法論は,溶融およびブリッジリングシステムを持つ分子への迅速なアクセスを可能にします.
- このアプローチは様々な天然製品や薬剤候補の合成に 期待を寄せている.
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