水素とデュテリオハロゲネーションのための分離可能で容易に扱えるハロフォスフォニウム前剤
Florian T Schevenels1,2, Minxing Shen1,2, Scott A Snyder1,2
1Department of Chemistry, The Scripps Research Institute , 130 Scripps Way, Jupiter, Florida 33458, United States.
Journal of the American Chemical Society
|May 3, 2017
まとめ
新しい反応剤は,実験室でのスケールでも,様々なアルケーンにHClとHBrの制御されたマルコフニコフ添加を可能にします. この方法は,制御された水解を用いたデュテラート添加 (DCl,DBr) も可能にします.
科学分野:
- 有機化学
- 合成方法論
背景:
- オレフィンに酸ハリドを加えることは,基本的な有機変換である.
- 既存の方法は,繊細な基板と小規模な合成で限界に直面しています.
- デュテラ酸ハリドの添加には,しばしば特殊な技術が必要です.
研究 の 目的:
- アルケンの制御されたマルコフニコフ製ヒドロハロゲン化のための多用途反応剤を開発する.
- 酸ハリド添加の現在の方法の限界に対処する,特に敏感な基板のために.
- 小規模合成とデュテラート添加のための信頼性の高い方法を確立する.
主な方法:
- ハロゲン化のための新種の反応剤の合成と応用.
- 多様な機能群と適合する軽度の反応条件の探索.
- 活性種と反応経路を明らかにするメカニズム研究
- D2Oを用いた制御されたデュテラート化ヒドロハロゲン化の方法の開発
主要な成果:
- この新しい反応剤は,軽度な条件下で,HClとHBrの選択的なマルコフニコフ添加を可能にします.
- この方法は,酸に敏感な部分とポリエネを含む様々な機能群に対する耐性を示す.
- 既存の技術と直接比較した実験室での成功
- DClとDBrを制御された水解で添加する簡単な方法の発見.
結論:
- 簡単に合成され,取り扱われる反応剤のクラスは,アルケンの水素化に顕著な進歩をもたらします.
- 開発された方法は,特に実験室規模の合成のために,改善された制御,選択性,および基板の範囲を提供します.
- メカニズム的な洞察は,活性化ヒドロハロゲネーション種を生成する水解の役割を明らかにし,デュテラート添加を可能にしました.
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