Kumagai, Naoya

写真a

Affiliation

Faculty of Pharmacy, Department of Pharmaceutical Sciences (Shiba-Kyoritsu)

Position

Professor

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Career 【 Display / hide

  • 2005.04
    -
    2006.03

    harvard University, Departmernt of Chemistry and Chemical Biology, Postdoctoral Fellow

  • 2006.04
    -
    2010.03

    The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assistant Professor

  • 2010.04
    -
    2010.12

    Institute of Microbial Chemistry, Laboratory of Synthetic Organic Chemnistry, Researcher

  • 2010.04
    -
    2017.03

    Rikkyo University, Department of Science, Adjunct Lecturer

  • 2011.01
    -
    2013.03

    Insttitute of Microbial Chemistry, Laboratory of Synthetic Organic Chemistry, Senior Researcher

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Academic Background 【 Display / hide

  • 1996.04
    -
    2000.03

    The University of Tokyo, Department of Pharmaceutical Sciences

    University, Graduated

  • 2000.04
    -
    2002.03

    The University of Tokyo, Graduate School of Pharmaceutical Sciences

    Graduate School, Completed, Master's course

  • 2002.04
    -
    2005.03

    The University of Tokyo, Graduate School of Pharmaceutical Sciences

    Graduate School, Completed, Doctoral course

Academic Degrees 【 Display / hide

  • The University of Tokyo, The University of Tokyo, Coursework, 2005.03

Licenses and Qualifications 【 Display / hide

  • Pharmacist, 2000.09

  • senior [first class] radiation protection supervisor, 2012.04

 

Books 【 Display / hide

  • Interplay of diamides and rare earth metals: Specific molecular spaces and catalytic activity

    Kumagai N., Shibasaki M., Designed Molecular Space in Material Science and Catalysis, 2018.01

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    A catalytic system comprising functionalized small diamides and rare earth metals (REs) exerts intriguing catalytic properties that are dictated by dynamic construction of flexible molecular spaces. The dynamic interaction of diamides and REs is characterized by broad applicability to distinct reaction systems as well as notable switchable catalysis. Structural modification of the diamide allows for enhanced intermolecular interactions to afford a self-assembled solid-phase catalyst with a specific molecular space that engages in heterogeneous asymmetric catalysis with a continuous-flow platform.

  • Chiral Bimetallic Lewis Acids

    Shibasaki M., Kumagai N., Topics in Organometallic Chemistry, 2018

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    Here, we review the utility of chiral bimetallic (multimetallic) Lewis acidic complexes in catalytic asymmetric transformations. Bimetallic complexes are endowed with dual catalytic functions that synergistically activate multiple substrates and functionalities. This cooperative activation mode is particularly effective for activating low reactivity substrates in a highly stereoselective manner without the aid of stoichiometric activating reagents. The privileged bimetallic catalysts presented here highlight the importance of catalyst design in the development of widely applicable catalytic systems.

Papers 【 Display / hide

  • Strategic Synthesis of Asymmetrically Substituted C4N4 Fluorophores

    Xu W., Kohei M., Shibasaki M., Kumagai N.

    Synthesis (Germany) (Synthesis (Germany))  53 ( 18 ) 3355 - 3360 2021.09

    ISSN  00397881

     View Summary

    C4N4 fluorophores comprise a recently disclosed new class of emissive organic molecules with modular synthetic capabilities. Herein, we report a new synthetic protocol toward asymmetrically di arylated C4N4 fluorescent materials. Direct monoarylation of 1-naphthol is exploited to suppress undesired diarylation and to provide a free phenolic hydroxy group for prospective linking to a molecule of interest. Installation of the second aromatic unit in order to acquire fluorescent properties is achieved by Suzuki-Miyaura cross-coupling.

  • Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes

    Saito A., Adachi S., Kumagai N., Shibasaki M.

    Angewandte Chemie - International Edition (Angewandte Chemie - International Edition)  60 ( 16 ) 8739 - 8743 2021.04

    ISSN  14337851

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    A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding NiII pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.

  • Highly Enantio- And Diastereoselective Synthesis of 1,2,3-Trisubstituted Cyclopropanes from α,β-Unsaturated Amides and Stabilized Sulfur Ylides Catalyzed by a Chiral Copper(I) Complex

    Pagire S.K., Kumagai N., Shibasaki M.

    ACS Catalysis (ACS Catalysis)     11597 - 11606 2021

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    The stereoselective preparation of 1,2,3-substituted cyclopropanes from α,β-unsaturated carbonyl compounds in the carboxylic acid oxidation state through Michael addition-initiated ring-closure reactions is a significant challenge in organic synthesis. Herein, the previously elusive catalytic asymmetric cyclopropanation of α,β-unsaturated amides with stabilized sulfur ylides has been efficiently accomplished utilizing a chiral Cu(I) complex. This Lewis acid catalytic system effectively converts a wide range of electron-deficient alkenes into the corresponding 1,2,3-trisubstituted cyclopropanes under mild reaction conditions in good to excellent yields with both high to excellent enantio- and diastereoselectivities. The resulting enantiomerically enriched cyclopropane amides can be readily diversified into promising synthetic intermediates such as β-aminocyclopropanecarboxylic acids with the facile recovery of the 7-azaindoline auxiliary without influencing the optical purity of the cyclopropane unit, which highlights the synthetic efficacy of this catalytic approach.

  • Direct Catalytic Asymmetric Addition of α-Fluoronitriles to Aldehydes

    Balaji P.V., Li Z., Saito A., Kumagai N., Shibasaki M.

    Chemistry - A European Journal (Chemistry - A European Journal)  26 ( 67 ) 15524 - 15527 2020.12

    ISSN  09476539

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    A fluorine-containing tetrasubstituted stereogenic center is a highly valued structural feature in medicinal chemistry. Herein, we describe the direct coupling of racemic α-fluoronitriles and aldehydes promoted by a chiral CuI/Barton's base catalytic system, delivering α-tetrasubstituted α-fluoro-β-hydroxynitriles with satisfactory stereoselection. The stereochemical course was positively biased by the combined use of asymmetrical achiral thiourea as a supplementary ligand for CuI, which significantly enhanced the stereoselectivity. Both aromatic and aliphatic aldehydes were implemented to provide densely and stereoselectively functionalized chiral building blocks with aliphatic and aromatic tails.

  • The Different Faces of [Ru(bpy)<inf>3</inf>Cl<inf>2</inf>] and fac[Ir(ppy)<inf>3</inf>] Photocatalysts: Redox Potential Controlled Synthesis of Sulfonylated Fluorenes and Pyrroloindoles from Unactivated Olefins and Sulfonyl Chlorides

    Pagire S.K., Kumagai N., Shibasaki M.

    Organic Letters (Organic Letters)  22 ( 20 ) 7853 - 7858 2020.10

    ISSN  15237060

     View Summary

    A cascade alkene sulfonylation that simultaneously forges C-S and C-C bonds is a highly efficient and powerful approach for directly accessing structurally diverse sulfonylated compounds in a single operation. The reaction was enabled by visible-light-mediated regioselective radical addition of sulfonyl chlorides to 2-arylstyrenes using fac[Ir(ppy)3] as a photocatalyst, demonstrating its unique role in a photocascade process to execute atom transfer radical addition (ATRA) followed by photocyclization. A new class of sulfonyl-substituted fluorenes and pyrroloindoles, which are useful in the field of photoelectronic materials and medicinal chemistry, was produced in excellent yields by this photocascade reaction. In contrast, the cyclization was interrupted when using the [Ru(bpy)3Cl2] catalyst having lower reduction potential, leading only to the formation of a C-S bond and the production of acyclic sulfonylated 2-arylstyrenes under identical reaction conditions. The synthetic utility of the present room-temperature photocatalysis is enhanced by the broad availability of bench-stable sulfonyl chlorides and unactivated olefins, thereby providing a cost-effective and broad-scope protocol.

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Research Projects of Competitive Funds, etc. 【 Display / hide

  • Strategic Molecular Design Aiming at Streamlined Chemical Transformations

    2020.04
    -
    2023.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, 熊谷 直哉, Grant-in-Aid for Scientific Research (B), Principal Investigator

 

Courses Taught 【 Display / hide

  • STUDY OF MAJOR FIELD (MOLECULAR DESIGN)

    2021

  • SEMINAR (MOLECULAR DESIGN)

    2021

  • RESEARCH FOR BACHELOR'S THESIS 1

    2021

  • PHARMACEUTICAL-ENGLISH SEMINAR

    2021

  • MOLECULAR DESIGN OF MEDICINE

    2021

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