C-OMe割れによる軽度かつリガンドフリーなNi触媒シリレーション
Cayetana Zarate1, Masaki Nakajima1, Ruben Martin1,2
1Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.
Journal of the American Chemical Society
|December 29, 2016
まとめ
この研究は,高価なリガンドなしで温和な条件下で炭素-酸素結合を断ち切る,アリルメチルエーサーのipso-silylationのための新しい触媒方法を導入しています. これは,新しい炭素-ヘテロ原子結合形成を可能にすることで,有機合成を進めます.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- 金属触媒によるCヘテロ原子結合の形成は有機合成において極めて重要です.
- アリルメチルエーサーは,C-OMe結合の割れが難しいため,価値のある,しかし挑戦的な結合パートナーです.
- C-OMe分裂の既存の方法は,しばしば厳しい条件,高価なリガンド,または狭い範囲によって制限されます.
研究 の 目的:
- C-OMe割れによるC-ヘテロ原子結合形成のための温和で効率的な触媒方法を開発する.
- C-OMe結合機能化に適した基板の範囲を拡大する.
- アリルエーテル変換の 新しい合成経路を探求する
主な方法:
- ニッケル触媒を用いたアリルメチルエーサーの触媒性ipso-silylation
- 軽度の反応条件で,外部リガンドは必要ありません.
- アニゾール,ベンジルメチルエーテル,ビニルメチルエーテルを含む様々な基板を使用した.
主要な成果:
- アリルメチルエーテルを 軽度な条件下で 触媒性イプソシリレーションに
- 挑戦的なアニゾール誘導体を含む幅広い基板の範囲を示した.
- オートゴナルシライレーションおよびさらなる誘導における応用を紹介した.
- 予備的なメカニズムの研究では,NiO-酸塩の複合中間物質が示唆された.
結論:
- 開発された方法は,C-OMe分裂によるC-ヘテロアトム結合形成に大きな進歩をもたらします.
- 反応の温和な条件と広い範囲は,有機合成のための貴重なツールです.
- この発見は,アリルメチルエーテルを触媒変換で利用するための新しい道を開く.
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
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