ロジウム・アリル・アルコキシド複合体へのアルデヒド挿入の直接観察
Christopher Krug1, John F Hartwig
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Journal of the American Chemical Society
|February 21, 2002
まとめ
Organorhodium ((I) コンプレックスは,アリルアルデヒドと反応し,非水性条件ではケトン,水性混合物ではダイアリルメタノールを生成する. 機械学的研究は,アルデヒドをロジウム-アリル結合に挿入することが重要なステップであることを明らかにしています.
科学分野:
- 有機金属化学 有機金属化学
- ロージウム触媒による触媒.
- オーガニック・シンセシス オーガニック・シンセシス
背景:
- Organorhodium ((I) 複合体は,有機変異に対してユニークな反応性を提供します.
- 反応メカニズムの理解は,効率的な合成方法論の開発に不可欠です.
研究 の 目的:
- アリルアルデヒドを含むオルガンホーディウム (((I)) 複合体の反応性を調査する.
- ケトンとダイアリルメタノールの形成のメカニズムを解明する.
- 二重挿入経路によるエステルの合成を調査する.
主な方法:
- オーガノロジウム ((I)) 複合体の合成と分離.
- 異なる溶媒条件 (非水性および水性THF) の下でアリルアルデヒドと複合体の反応.
- 運動イソトープ効果と中間特性を含むメカニズム研究.
主要な成果:
- ケトンは,アルデヒドの挿入とβ-ヒドリドの除去を経由して,非水性条件下で良好な収量で形成されます.
- ディアリルメタノールは,アルデヒドの挿入と水解によってTHF/水混合物においてのみ生成されます.
- rodium diarylmethoxide の中間物質が直接観察され,特徴づけられました.
- エステルは,過剰なアルデヒドによる二重挿入とβ-水素除去配列によって形成されます.
結論:
- 反応経路は,溶媒条件によって決定され,ケトンまたはダイアリルメタノールにつながる.
- ロジウム-アリル結合へのアルデヒドの挿入が主なステップです.
- 観察された中間反応およびその後の反応は,β-水素の除去および/または水解を含むメカニズムをサポートしています.
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