Development of Domino Catalyst merged with organic synthesis and polymerization

2021 Fiscal Year Final Research Report

• Project Area: Hybrid Catalysis for Enabling Molecular Synthesis on Demand
• Project/Area Number: 17H06451
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Hou Zhaomin 国立研究開発法人理化学研究所, 開拓研究本部, 主任研究員 (10261158)
• Project Period (FY): 2017-06-30 – 2022-03-31
• Keywords: 希土類金属 / C-H結合活性化 / 不斉触媒 / 非極性オレフィンと極性オレフィンの共重合 / 自己修復材料 / シクロペンタジエニル基 / 銅触媒

Outline of Final Research Achievements

This project aimed to develop new catalysts, new reactions and new functional materials superior or complementary to those existing. By using half-sandwich rare-earth catalysts, we have achieved for the first time the terpolymerization of ethylene and two different methoxyaryl-substituted propylenes in a controlled domino reaction fashion, which afforded a new family of functional polyolefins with excellent self-healing property. We have synthesized a series of chiral half-sandwich rare-earth alkyl complexes that show excellent enantioselectivity and activity in various transformations such as asymmetric dearomative annulation of quinolines with alkynes and asymmetric exo-selective annulation of imidazoles with 1,1-disubstituted alkenes via C－H activation. We have achieved efficient and selective difunctionalization of imines via CO2 activation by an N/B Lewis pair under copper catalysis.

Free Research Field

有機金属化学　触媒化学　有機合成化学　高分子化学

Academic Significance and Societal Importance of the Research Achievements

本研究の成果は、有機金属化学や触媒化学、有機合成化学、高分子合成化学などの基礎科学分野の新しいフロンティアの開拓のみならず、新たな知財の形成や新産業の創出にもつながることが期待できる。例えば、本研究で創製された新規自己修復ポリマーは、空気中だけでなく、水や酸、アルカリ性水溶液中でも優れた自己修復性能を示し、従来のものでは見られない実用性の高い新機能性材料として多方面から大きな期待が寄せられている。