Development of heterogeneous catalyst systems based on bifunctional chiral ligands and finely designed metal nanoparticles

2020 Fiscal Year Final Research Report

• Project/Area Number: 17KK0101
• Research Category: Fund for the Promotion of Joint International Research (Fostering Joint International Research)
• Allocation Type: Multi-year Fund
• Research Field: Transition State Control
• Research Institution: The University of Tokyo
• Principal Investigator: Miyamura Hiroyuki 東京大学, 大学院理学系研究科(理学部), 助教 (00548943)
• Project Period (FY): 2018 – 2020
• Keywords: 不均一系触媒 / 超分子触媒 / 遷移状態制御 / 不斉合成 / フロー反応 / ナノクラスター / ナノ粒子 / キラル触媒

Outline of Final Research Achievements

To develop the first heterogeneous supramolecular catalysts in the world, an chiral supramolecular cluster Ga416 was introduced into cross-linked polymers with cationic functionalities. These heterogeneous supramolecular catalysts were used in aza-Prins and aza-Cope reactions. They showed high durability and maintained high turnovers for long periods of time. In addition, the newly developed catalysts showed enhanced activity and robustness compared to those exhibited by the corresponding soluble cluster catalyst. An enantioenriched cluster was also immobilized to enable asymmetric catalysis, and activity and enantioselectivity were maintained during recovery and reuse and in a continuous-flow process. The ammonium cations in the polymers affected stability, reactivity and enantioselectivity, which is consistent with the hypothesis that the cationic moieties in the polymer interact with cluster as an exohedral protecting shell, thereby influencing their catalytic performance.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

研究代表者はUC Berkeleyの共同研究グループとともに、世界で初めての不均一系超分子触媒を開発し、本触媒が不斉合成や連続フロー合成で有効に機能することを見出した。本研究により、高分子に固定化された超分子触媒の人工酵素としての新たな活性発現のメカニズムを発見した。また、本研究で新たに開発した不均一系触媒は連続フロー系における不斉合成が可能であり、次世代の有機合成反応として期待される、医薬品等の連続フロー合成の実現に直結する。さらに、人工膜酵素や人工生命創出への展開も期待される。