高分子固定化不斉触媒の開発と不斉反応への応用

摘要

高分子固定化キラル1,2－ジアミンと高分子固定化キラル第四級アンモニウム塩の合成法と不斉rn反応への応用についてまとめた．フェノール性ヒドロキシル基を導入したキラル1,2-ジアミンを用い，高rn分子中の特定の位置にキラル1,2-ジアミンを有するポリマーを高分子反応またはラジカル重合により合成rnした．キラル第四級アンモニウム塩の高分子固定化はスルホネートを有する高分子担体とのイオン交換反rn応またはラジカル重合により行い，イオン結合による高分子固定化キラル第四級アンモニウム塩の合成にrn成功した．rn高分子固定化不斉触媒を用いたケトンの不斉水素化反応，水系でのケトンやイミンの水素移動型不斉還rn元反応，グリシン誘導体の不斉アルキル化反応，シクロペンタジエソとケイ皮酸アルデヒドのDiels-Al-der反応は速やかに進行し，目的の光学活性化合物を高立体選択性で定量的に得ることに成功した．高分子固定化不斉触媒は簡単に回収することができ，数回から十数回の再使用が可能であった．%Polymer-supported chiral 1,2-dianune and chiral 1,2-diamine monosulronamide were successtully synthesized by polymer reaction and by polymerization. Sulfonic acid quaternary ammonium and phosphonium salts were introduced into the support polymer to control the hydrophilic-hydrophobic balance for asymmetric reactions in water. Polymer-supported chiral organocatalysts with quaternary ammonium salt were successfully synthesized by ion exchange reaction of the quaternary ammonium salt with sulfonated support polymer. These polymer-supported chiral catalysts were utilized in asymmetric hydrogenation, transfer hydrogenation, alkylation and Diels-Alder reactions. Optically active products were quantitatively obtained with high enantioselectivity. In some cases, the enantioselectivity of polymer-supported chiral catalysts was superior to that of the corresponding chiral molecular catalyst. Polymer-supported chiral catalysts were recovered and reused without significant loss of the catalytic activity.