ホイドラジンとアジドは,金属触媒によるオレフィンのヒドロヒドラジネーションとヒドロアジネーションを経由して生成される
Jérôme Waser1, Boris Gaspar, Hisanori Nambu
1Laboratorium für Organische Chemie, ETH Zürich, Hönggerberg HCI-H335, 8093 Zürich, Switzerland.
Journal of the American Chemical Society
|August 31, 2006
まとめ
コバルトとマンガンは,オレフィンに対する新しい水素酸化と水酸化反応を触媒化する. これらの方法は,機能化されたアミンと多用途のアジド中間物質への効率的な経路を提供します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- カタリシス カタリシス カタリシス
- 合成方法論 合成方法論
背景:
- オレフィンのヒドロアミネーションは,有機合成における重要な変換である.
- 既存の方法は,しばしば機能化された基板または厳しい条件を必要とします.
研究 の 目的:
- オレフィンの新しいコ-およびMn触媒による水素水解化および水酸化反応を開発する.
- 機能化されたアミンおよび関連化合物への効率的で多用途な合成経路を確立する.
主な方法:
- オレフィン機能化のためのコバルト (Co) とマンガン (Mn) の触媒を使用した.
- 水素源としてシランを用い,窒素源としてアゾジカルボキシラートまたはスルフォニルアジドを使用した.
- ディ-テルト-ブチルアゾジカルボキシラートを用いた様々なオレフィンの水素水酸化を調査した.
- ソルフォニルアジドとテルトブチル水酸化物を用いてオレフィンの水酸化を発展させた.
主要な成果:
- 幅広いオレフィン (モノ-,二-,三-,および四位置換) の効率的な水素水素化が達成され,優れた機能群耐性があります.
- モノ-,二-,三置換オレフィンの水酸化を成功裏に実施し,汎用性のあるアルキルアジド中間産物を得ました.
- 取得したアルキルアジドが,容易に自由アミンまたはトリアゾールに変換できることを実証した.
- 予備的なメカニズムの研究は,速度を制限するヒドロコバルト化に続いてアミネーションが進み,潜在的に中間基が関与することを示唆しています.
結論:
- 開発されたCoおよびMn触媒反応は,オレフィン機能化のための強力な新しい方法を提供します.
- これらの反応は,範囲,機能グループ耐性,使いやすさという点で明確な利点を提供します.
- 生成されたアジド中間産物は,アミンとトリアゾール合成のための貴重な前駆体として機能します.
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