サイズ制御可能な大容量の"コーン"リガンドに基づく単体および二元混合ディオルガノキュプレート
Mikinao Ito1, Daisuke Hashizume, Takeo Fukunaga
1Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Journal of the American Chemical Society
|December 1, 2009
まとめ
研究者は,大量のリンドリンガンドを使用して,新しい混合ディオルガノコッパー ((I)) 複合体を合成しました. その結果生じるモノメリック複合体は,2つの異なる有機群を選択的に結合させ,有機金属化学を進める.
科学分野:
- 有機金属化学 有機金属化学
- 合成化学 合成化学とは
- カタリシス カタリシス カタリシス
背景:
- ダイオルガノコッパー (diorganocopper) 複合体は,有機合成における重要な反応剤である.
- 混合ダイオルガノコッパー ((I) 複合体の分離と特徴付けは,その反応性と不安定性のために合成上の課題を提示します.
研究 の 目的:
- 新型,分離可能な混合ダイオルガノコッパー ((I)) 複合体を合成し,構造的に特徴づけること.
- クロスカップリング反応におけるこれらの複合体の反応性を調査する.
主な方法:
- 溶融リングのオクタ-R-置換されたs-ヒドリンダセンの骨格を基にした,ボリュームの大きいリンドリンガンドの合成.
- RindLiが銅 (I) ブロミド (CuBr) と反応して,オルガノブロモキュプラートのジマーまたはモノマーを形成する.
- ブロムをリチウムトリメチルシリラセチリドに置き換えることで,混合アリル (((アルキニル) 銅 (((I)) 複合体を生成する.
主要な成果:
- 成功して合成し,構造的に特徴付けられた二次および単体アリル (alkynyl) 銅 (copper) I) 複合体.
- コンプレックスBは,モノメリック混合ディオルガノキュプラート (LiCuRR') で,同種の最初の分離可能な例です.
- 複合体Bは,銅に結合した2つの異なった有機群の選択的酸化クロスカップリングを示した.
結論:
- リンド・リガンドのステリックの大部分は,モノメリックまたは二重性カップレートの形成を決定する.
- 単離可能な混合ダイオルガノキュプラートモノマーの開発は,銅媒介の有機変換の範囲を広げています.
- これらの新しい複合体は,選択的クロスカップリング反応のためのプラットフォームを提供し,合成の有用性を高めます.
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