Development of Novel Immobilization Methods for Multicomponent Asymmetric Catalyst (MAC)

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  • 複数の構成要素を持つ不斉触媒“Multicomponent Asymmetric Catalyst(MAC)”の固定化
  • フクスウ ノ コウセイ ヨウソ オ モツ フセイ ショクバイ Multicomponent Asymmetric Catalyst MAC ノ コテイカ

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Abstract

Several methodologies for the immobilization of multicomponent asymmetric catalysts (MACs), which consist of two molecules of 1,1'-bi(2-naphthol)(BINOL) and two metals, have been developed. In the first place, Al-Li-bis(binaphthoxide)(ALB) and/or Ga-Na-bis(binaphthoxide)(GaSB) catalysts were introduced to the dendrimers and soluble polymers containing dendron units. Since these dendritic molecules require multi-step synthesis, efficient syntheses of the spherical particles that function like dendrimer-supported catalysts were realized by use of a micelle-derived polymer (MDP) and a monolayer-protected metal cluster (MPC). Secondly, a novel approach based on the use of “catalyst analogue” is found to be effective to position the ligands suitably on the polymer backbone. Thirdly, utilizing metal-bridged polymers, a simple and efficient method for immobilization without the need for a polymer support has also been realized. Heterogeneous ALB, GaSB and μ-oxodititanium complexes thus obtained have been used as catalysts for the asymmetric Michael addition and the asymmetric carbonyl-ene reactions, respectively. The catalysts displayed high activity, affording the corresponding products with high enantiomeric excesses. These catalysts could be recovered and reused.

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