Pd(II) -硫黄アミド酸塩のPd-N結合への可逆アルケンの挿入と,触媒性アミダ化反応への影響
Paul B White1, Shannon S Stahl
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA
Journal of the American Chemical Society
|October 20, 2011
まとめ
パラジアム-窒素結合へのアルケンの挿入は,酸化性アミダ化に不可欠である. 電子が豊富なアミダートは,この重要な反応段階を加速し,効率的な産物形成につながります.
科学分野:
- 有機金属化学 有機金属化学
- カタリシス カタリシス カタリシス
- オーガニック・シンセシス オーガニック・シンセシス
背景:
- パラジアム-窒素結合へのアルケンの挿入は,パラジアム触媒による酸化アミデーションの基本的なステップです.
- この反応に影響を与える要因を理解することは,より効率的な触媒システムの開発の鍵です.
研究 の 目的:
- パラジウム (((II) -硫黄胺酸複合物を準備し,特徴づけるために.
- Pd-N結合へのアルケンの挿入のメカニズムを調査する.
- 挿入反応に対する電子効果の影響を調査する.
主な方法:
- 明確に定義されたPd(II) -硫黄胺酸複合物の合成.
- Pd-アミデートとPd-アルキル中間物の結晶学的な特徴.
- アルケンの挿入に関する運動および熱力学的研究.
- 様々なアミド酸リガンドを用いた電子効果の研究.
主要な成果:
- Pd (II) -硫黄胺酸複合体は,結合したアルケンの挿入を受けます.
- その結果得られたPd-アルキル種は結晶学的に特徴づけられた.
- アルケンの挿入は可逆的ですが,O(2) は酸化アミネーション製品への完全な変換を促します.
- 電子に富んだアミデットは,運動学的に,熱力学的に,アルケンのPd-N結合への挿入を好みます.
結論:
- Pd-N結合へのアルケンの挿入は,可逆的なプロセスです.
- 電子が豊富なアミダートは,アルケンの挿入の速度と好意性を高めます.
- パラジウムで触媒化された酸化アミダーションは,最適化されたアミダートリガンドで効率的に達成できます.
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