2021 Fiscal Year Final Research Report
New Development of Coordination Asymmetry Based on Precise Control of Metal Centered Chirality
| Project Area | Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules |
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| Project/Area Number |
16H06509
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| Research Category |
Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | The University of Tokyo |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
馬越 啓介 長崎大学, 工学研究科, 教授 (20213481)
松下 信之 立教大学, 理学部, 教授 (80219427)
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| Project Period (FY) |
2016-06-30 – 2021-03-31
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| Keywords | 配位アシンメトリー / 金属中心キラリティー / 不斉誘導 / 不斉触媒反応 |
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| Outline of Final Research Achievements |
This study has aimed to establish design and synthetic methods for asymmetric coordination spheres in metal complexes, to establish asymmetric induction methods, to stabilize the configuration of chiral centers, and to pioneer asymmetric catalytic reactions and chiral materials. The following research results were obtained and published in international journals.
(1) Asymmetric induction and stabilization of tetrahedral chiral zinc complexes with unsymmetric achiral tridentate ligands, (2) porous supramolecular metal complexes by self-assembly of helical macrocyclic metal complexes: asymmetric molecule adsorption and construction of chiral environment field, and (3) asymmetric induction of enzyme-like metal centers using chiral DNA molecules as templates
In particular, the result of (1) is the first example in the world of asymmetric induction and configuration stabilization of a Werner-type substitution-active chiral-at-metal complex.
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| Free Research Field |
超分子化学
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| Academic Significance and Societal Importance of the Research Achievements |
本研究は、置換活性金属中心の「不斉誘導」と「絶対配置の安定化」という最も困難な課題を革新的に解決し、「不斉金属の化学」の大きなブレークスルーにつながった。特に、四面体型キラル亜鉛錯体の高選択的不斉誘導と驚異的な安定化から得られた知見は、教科書に見られる置換活性金属に関する常識を根底から覆すものであり、本領域を先導するランドマークとなった。この結果により発展した非対称な集積・空間・電子系アシンメトリーは、明確に定義された配向と異方性に基づく新物性や新機能に発展することが期待され、周辺分野である触媒化学、超分子錯体化学、生体関連化学、材料科学等の物質科学へ大きな波及効果をもたらすことが期待される。
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