オキシホスフォニウム-アルキンサイクル添加反応: 1,2-オキシホスフェットと6基のリンヘトロサイクルの可逆的形成
Pawel Löwe1, Milica Feldt2, Marius A Wünsche1
1Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 30, 48149 Münster, Germany.
Journal of the American Chemical Society
|May 5, 2020
まとめ
オキシホスフォニウムイオンはアルキンと [2 + 2] サイクル添加で反応し,新しい1,2-オキシホスフェットイオンを形成する. これらの中間物質は,さらに価値ある6基のリンヘテロサイクルに変換され,合成の可能性を広げることができます.
科学分野:
- 有機化学
- オルガノフォスファース化学
- メイングループ化学
背景:
- アルキンとカルボニル化合物を含むメタテシス反応は,有機合成の礎石である.
- アルキンの同電子主群R2EO化合物の反応性は,ほとんど未研究のままである.
- オキシホスフォニウムイオンは,カルボニル化合物の同胞として機能する.
研究 の 目的:
- オキシホスフォニウムイオンとアルキンの間のサイクル添加反応を調査する.
- 合成されたリン含有ヘテロサイクルの有用性を探求する.
- これらのシステムにおける酸素原子の移転を制御する電子的要因を解明する.
主な方法:
- オキシホスフォニウムイオンと様々なアルキンの間の [2 + 2] サイクル添加反応.
- 1,2-オキシホスフェットイオンの分離と構造的特徴.
- ヘテロサイクルの熱環開きにより,ヘテロジンの中間物質が形成される.
- ヘテロ・ディエルス・アルダー反応は6基のリンヘトロサイクルを合成する.
- 反応メカニズムと置換物の効果を研究するための量子化学的計算.
主要な成果:
- オキシホスフォニウムイオンとアルキンが1,2-オキシホスフェットイオンを形成するために [2 + 2]サイクル添加を成功させた.
- これらの新しいストレントのリン-酸素ヘテロサイクルの分離と完全な構造的特徴付け.
- ヘテロジンの中間物質への熱環開封の実証
- その後のヘテロ・ディエルス・アルダー反応により,多様な6基のリンヘトロサイクルが合成された.
- 量子化学的な計算により,酸素原子の移転エネルギーに対する代替効果の洞察が得られた.
結論:
- オキシホスフォニウムイオンは,アルキンの [2 + 2] サイクル添加で反応するパートナーであり,独特の1,2-オキシホスフェットイオンを生成する.
- これらのリンヘテロサイクルは,より複雑なリンを含むリングシステムを構築するための多機能な前駆体として機能します.
- この研究は,有機リン化学とメイングループ元素の変換のための合成ツールボックスを拡張します.
![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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