非活性アルケンのリガンド制御されたIr-触媒化されたRegiodivergent Oxyamination
Honghui Lei1, John H Conway1, Caleb C Cook1
1Department of Chemistry , Columbia University , New York , New York 10027 , United States.
Journal of the American Chemical Society
|July 17, 2019
まとめ
この研究では,イリジウム触媒によるオキシアミネーション反応を導入し,活性化されていないアルケンから貴重なラクトームとラクトンを生成します. このプロセスは,調節可能なイリジウム複合体を介して,異なるリングサイズの制御された合成を可能にします.
科学分野:
- 有機金属化学
- 合成有機化学
- カタリシス
背景:
- 内分子酸化反応は,ヘテロサイクル化合物の合成に不可欠である.
- 活性化されていないアルケンの地域選択的方法の開発は,依然として合成の課題です.
- イリジウム触媒は,C-H機能化および関連する変換にユニークな反応性を提供します.
研究 の 目的:
- 活性化されていないアルケンの新種の分子内酸化を 開発する.
- γ-ラクタム, γ-ラクトン,および δ-ラクタムの地域別合成を達成する.
- 反応メカニズムを解明し,主要な中間物質を特定する.
主な方法:
- イリジウム (III) 複合体によって触媒化された分子内オキシアミネーション戦略を使用した.
- 電子的に調節可能なサイクロペンタジニルイリジウム (III) 複合体を使用し,地域選択性を制御する.
- 5 - エクソおよび6 - エンドオサイクルを含む反応経路の調査.
主要な成果:
- 活性化されていないアルケーンから有価なγ-ラクタム,γ-ラクトン,およびδ-ラクタムを成功して合成した.
- イリジウム触媒を調節することで,オキシアミネーションプロセスを制御することが示された.
- イリジウム (V) 窒素から派生した主要な [3.1.0] バイサイクル中間物質を含む反応機構を提案した.
結論:
- 多様なラクトームとラクトン構造にアクセスするための多用途のIr (III) 触媒による地域分散型オキシアミネーションを開発した.
- 地域選択性は,触媒設計によって効果的に制御され,異なるリングサイズへのアクセスを可能にします.
- 提案されたメカニズムは,新しいバイサイクルの中間物質の形成を強調し,Ir-触媒化された変換の理解を進める.
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