2021 Fiscal Year Final Research Report
Ligand Design for Catalytic Asymmetric C-H Bond Functinalization
| Project/Area Number |
18H03906
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Review Section |
Medium-sized Section 33:Organic chemistry and related fields
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| Research Institution | Hokkaido University |
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Principal Investigator |
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| Project Period (FY) |
2018-04-01 – 2022-03-31
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| Keywords | 不斉合成 / C-H活性化 / 非古典的水素結合 / ロンドン分散力 / 銅触媒 / アリル化 / ホスフィン配位子 |
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| Outline of Final Research Achievements |
<1. Application of prolinol-phosphine ligands> We developed new reactions and ligands focusing on non-classical hydrogen bonding with sp3-C-H bonds. Furtheremore, copper-catalyzed asymmetric Kinugasa reaction and silver-catalyzed isocyanoacetate asymmetric Aldol reactions were developed. We also clarified the importance of sp3-C-H/π interaction in the study of Ir-catalyzed hydrogen transfer asymmetric reduction of ketones.
<2. Application of phenol-carbene ligands> We developed a copper-catalyzed reaction between organic boron and silicon compounds. These studies led to the discovery of a visible light-driven copper-catalyzed asymmetric allyl-position acylation reaction.
<3. Pd-catalyzed asymmetric allylation of alkylazaarene> Highly enantioelectivities have been achieved with a cleft-type monodentate diamidophosphite ligand.
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| Free Research Field |
有機金属化学
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| Academic Significance and Societal Importance of the Research Achievements |
本研究は酸性度の異なるsp-C-H、sp2－C－H、sp3－C－Hを対象とした総合的な取り組みにおいて、触媒と反応基質の間に働く非共有結合性相互作用の重要性に光を当てることで、化学反応の原理を深く理解することに貢献した。不斉配位子・触媒の設計によって立体選択性を追求しつつ、反応機構を実験と理論化学の組み合わせで検証することによって、触媒設計・反応設計の発展に大きく貢献した。非極性のsp3－C－Hがsp3－C－H/O水素結合やロンドン分散力を通じて化学反応の促進や制御に大きく関わり、従来の立体障害の概念とは真逆の効果を誘起しうることを示したことの意義は特に顕著である。
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