Hanaya, Kengo

写真a

Affiliation

Faculty of Pharmacy, Department of Pharmaceutical Sciences 有機薬化学講座 （Shiba-Kyoritsu）

Position

Assistant Professor/Senior Assistant Professor
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Academic Degrees 【 Display / hide 】

  • 博士（薬学）, Tokyo University of Science, Coursework, 2012.03

    Design and Synthesis of Biomedical Tools and Metalloprotease Inhibitors Based on Chemical Properties of 8-Quinolinol and Their Sulfonates

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Papers 【 Display / hide 】

  • Single-Step N-Terminal Modification of Proteins via a Bio-Inspired Copper(II)-Mediated Aldol Reaction

    Hanaya K., Yamoto K., Taguchi K., Matsumoto K., Higashibayashi S., Sugai T.

    Chemistry - A European Journal （Chemistry - A European Journal)  28 （ 47 ）  2022.08

    Research paper (scientific journal), Lead author, Corresponding author, Accepted,  ISSN  09476539

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    The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein-based materials. The N-terminus is a promising target for single-site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)-mediated aldol reaction with 2-pyridinecarboxaldehyde (2-PC) derivatives is proposed as an operationally simple method to selectively modify the N-terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N-terminal amino acids by complexation with an imine of the N-terminal amino acid and 2-PCs, realizing the selective formation of the nucleophilic intermediate at the N-terminus. This results in a stable carbon-carbon bond between the 2-PCs and the α-carbon of various N-terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity.

  • One-Step Synthesis of Acylborons from Acyl Chlorides through Copper-Catalyzed Borylation with Polystyrene-Supported PPh<inf>3</inf>Ligand

    Nakahara M., Kurahayashi K., Hanaya K., Sugai T., Higashibayashi S.

    Organic Letters （Organic Letters)  24 （ 30 ） 5596 - 5601 2022.08

    Research paper (scientific journal), Accepted,  ISSN  15237060

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    We developed a one-step synthesis of acylborons from both readily available acyl chlorides and bis(pinacolato)diboron through copper(I)-catalyzed borylation. Under the reaction conditions using tBuOLi, polystyrene-supported triphenylphosphine as a copper ligand was found to promote the borylation of acyl chlorides while suppressing alcoholysis. This method enables the facile synthesis of potassium acyltrifluoroborates.

  • Synthesis of 1H-2-Benzopyran-5,8-dione Skeleton through a Cascade Reaction between Benzoquinone and β-Ketoester

    Nakahara M., Ohtsu H., Kawano M., Hanaya K., Sugai T., Higashibayashi S.

    Chemistry Letters （Chemistry Letters)  51 （ 4 ） 356 - 359 2022.04

    Research paper (scientific journal), Accepted,  ISSN  03667022

    　View Summary

    The 1H-2-benzopyran-5,8-dione structure was synthesized by a cascade reaction through Michael addition, elimination of HBr, and O-alkylation between a dibromobenzoquinone derivative and β-ketoesters under basic conditions. The reaction using potassium carbonate and 18-crown-6 in THF was the best condition, giving 1H-2-benzopyran-5,8-dione derivatives in good yields. The UV-vis absorption spectrum and cyclic voltammogram of the synthesized 1H-2-benzopyran-5,8-dione derivative were measured, clarifying the photophysical and redox properties.

  • 1,2-Rearrangement from o-Quinols to Multisubstituted Catechols via Retro Diels-Alder Reaction of o-Quinol Dimers

    Hashimoto R., Hanaya K., Sugai T., Higashibayashi S.

    Bulletin of the Chemical Society of Japan （Bulletin of the Chemical Society of Japan)  95 （ 4 ） 663 - 672 2022

    Research paper (scientific journal), Accepted,  ISSN  00092673

    　View Summary

    The 1,2-rearrangement of o-quinols has been a long-standing unsolved problem since 1958. Although the rearrangement is expected to be useful for syntheses of catechol derivatives, it is hampered by many competing reactions and has not been developed as a useful methodology. Here, we succeeded in settling this problem by a first systematic thorough investigation, establishing the 1,2-rearrangement as a cascade reaction with a retro Diels-Alder reaction from o-quinol dimers. This is a useful strategy for syntheses of substituted catechols used as synthetic building blocks for bioactive compounds and material molecules. o-Quinol dimers were synthesized by improved oxidative hydroxylation of substituted phenols followed by spontaneous Diels-Alder reaction. The dimers then underwent the retro Diels-Alder reaction to regenerate the o-quinols followed by 1,2-rearrangement under neutral heating conditions at an appropriate temperature depending on the migratory substituent, furnishing substituted catechols in good yields. The competing reactions such as an elimination of a substituent or α-ketol rearrangement were minimized by controlling the reaction temperature.

  • Copper-Catalyzed Stereoselective Borylation and Palladium-Catalyzed Stereospecific Cross-Coupling to Give Aryl C-Glycosides

    Kurahayashi K., Hanaya K., Sugai T., Hirai G., Higashibayashi S.

    Chemistry - A European Journal （Chemistry - A European Journal)  29 （ 6 ）  2022

    Research paper (scientific journal), Accepted,  ISSN  09476539

    　View Summary

    Metabolically stable C-glycosides are an essential family of compounds in bioactive natural products, therapeutic agents, and biological probes. For their application, development of synthetic methods by connecting glycosides and aglycons with strict stereocontrol at the anomeric carbon, as well as with high functional-group compatibility and environmental compatibility is a pivotal issue. Although Suzuki–Miyaura-type C(sp3)−C(sp2) cross-coupling using glycosyl boronates is a potential candidate for the construction of C-glycosides, neither the cross-coupling itself nor the facile synthesis of the coupling precursor, glycosyl boronates, have been achieved to date. Herein, it was succeeded to develop a copper-catalyzed stereoselective one-step borylation of glycosyl bromides to glycosyl boronates and palladium-catalyzed stereospecific cross-coupling of β-glycosyl borates with aryl bromides to give aryl β-C-glycosides, in which the β-configuration of the anomeric carbon of the glycosyl trifluoroborates is stereoretentively transferred to that of the resulting aryl C-glycosides.

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Papers, etc., Registered in KOARA 【 Display / hide 】

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Presentations 【 Display / hide 】

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

  • 一時的配向基を用いた遷移金属触媒反応によるタンパク質ペプチド結合の化学修飾

    2021.04
    -
    2024.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (C), Principal investigator

  • ボロン酸を用いるクロスカップリング反応を基盤としたタンパク質化学修飾法の開発

    2019.04
    -
    2021.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, Grant-in-Aid for Early-Career Scientists , Principal investigator

  • スルホン酸エステルを母核とした刺激応答性リンカーの開発とプロドラッグへの応用

    2016.04
    -
    2019.03

    JAPAN SOCIETY FOR THE PROMOTION OF SCIENCE, Grant-in-Aid for Scientific Research, KENGO HANAYA, Research grant, No Setting

  • 刺激応答性リンカーの創製に向けたアミノスルホン酸エステルの分子内環化反応の開発

    2016.04
    -
    2017.03

    THE JAPAN SCIENCE SOCIETY, SASAKAWA SCIENTIFIC RESEARCH GRANT, KENGO HANAYA, Research grant, Principal investigator

  • 酵素触媒を活用した不斉誘導体化試薬の創製 （超高感度化と効率的供給法の開発）

    2015.04
    -
    2016.03

    日本私立学校振興・共済事業団, The Science Research Promotion Fund, Kengo Hanaya, Principal investigator

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Courses Taught 【 Display / hide 】

  • STUDY OF MAJOR FIELD: (ORGANIC AND BIOCATALYTIC CHEMISTRY)

    2022

  • SEMINAR: (ORGANIC AND BIOCATALYTIC CHEMISTRY)

    2022

  • RESEARCH FOR BACHELOR'S THESIS 1

    2022

  • RESEARCH APPARATUS LABORATORY COURSE

    2022

  • PHARMACEUTICAL-ENGLISH SEMINAR

    2022

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