フォスフィレン-フォスフィニデンの再配列による一時的なビニルフォスフィニデン

Liu Leo Liu¹, Jiliang Zhou¹, Levy L Cao¹

¹Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.

Journal of the American Chemical Society

|December 23, 2017

まとめ

新しい結晶2H-フォスフィレンが合成され,ビニルフォスフィニデンの中間体として作用することが示された. この中間物質は,C-N結合の分裂と芳香C-C結合への挿入を含むユニークな反応を経験します.

科学分野:

オルガノフォスファース化学
合成有機化学
炭酸塩化学

背景:

フォスフィーレンは,限られた安定性を有する3つ構成のリンを含むヘテロサイクルである.
ビニルフォスフィニデンは,新しいP-C結合を形成するために不可欠な高度に反応性の中間物質です.

研究の目的:

安定した結晶2H-フォスフィレンを合成する
ビニルフォスフィニデンの源として合成されたフォスフィレンの反応性を調査する.
リン基介質を含む新しい反応を探求する.

主な方法:

電気性ダイミドカルベンのターチルフォスファルキンとの反応
合成されたフォスフィレンの熱分解.
C6Cl4O2と (tht) AuClとの反応

主要な成果:

室温に安定する結晶2H-フォスフィレン (1) が成功裏に製造された.
化合物1は,ビニルフォスフィニデンの中間物質を生成するために再編成されます.
熱解はC−N結合分裂を誘導し,C6Cl4O2と (tht) AuClとの反応はそれぞれ酸化とC−C結合の挿入につながった.

結論:

合成されたフォスフィレンは,ビニルフォスフィニデンの安定した前駆体として機能する.
この研究は,Büchner 環膨張反応の最初のリン類型を提示する.
有機リン合成と反応性中間化学の新たな道が開かれている.

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