Higashibayashi, Shuhei



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


Associate Professor

Licenses and Qualifications 【 Display / hide

  • 甲種危険物取扱者, 2004.08


Research Areas 【 Display / hide

  • Organic chemistry


Books 【 Display / hide

  • Control of inversion kinetics of bowl-shaped aromatic compounds

    Higashibayashi S., Kinetic Control in Synthesis and Self-Assembly, 2018.01

     View Summary

    Bowl inversion property of bowl-shaped aromatic compounds, buckybowls, is reviewed in this chapter. Bowl inversion kinetics of many kinds of buckybowls have been extensively investigated including pristine buckybowls such as corannulene, sumanene, diindenochrysene, and extended buckybowls, substituted buckybowls, and heterobuckybowls. The magnitude of bowl inversion barrier was altered in very wide range depending on the kinds of buckybowl skeleton, the extension of bowl π-conjugation, the substituents, the heteroatoms, and the redox. Introduction of substituents changed the barriers in a few kcal/mol range and the correlation between the bowl inversion barriers and bowl depths was elucidated in corannulene and sumanene skeletons. Introduction of heteroatoms substantially changed the magnitude of inversion barrier without changing bowl sizes. Chiral buckybowls with stable bowl chirality were also achieved by realizing the high bowl inversion/racemization barrier by introduction of substituents or heteroatoms. Based on these extensive studies, bowl inversion kinetics can be controlled by these factors.

  • Kinetic Control in Synthesis and Self-Assembly

    Shuhei Higashibayashi (Ed. M Numata, S. Yagai, T. Hamura), Elsevier, 2018

    Scope: Chapter 4, “Control of Inversion Kinetics of Bowl-Shaped Aromatic Compounds”,  Contact page: 65-96

  • Chemical Science of π-Electron Systems

    Shuhei Higashibayashi, Hidehiro Sakurai, etc. (Eds. T. Akasaka, A. Osuka, S. Fukuzumi, H. Kandori, Y. Aso), Springer, 2015

    Scope: Chapter 6, "Chiral Sumanene, Triazasumanene, and Related Buckybowls",  Contact page: 91-106

  • Polycyclic Arenes and Heteroarenes: Synthesis, Properties, and Applications

    Shuhei Higashibayashi, Hidehiro Sakurai, etc. (Ed. Q. Miao), Wiely-VCH, 2015

    Scope: Chapter 3, "Growing Buckybowl Chemistry",  Contact page: 61-84

  • CSJカレントレビュー, 未来材料を創出するπ電子系の科学

    櫻井英博, 東林修平, 他, 化学同人, 2013

    Scope: 第1章 精密合成が拓くπ電子科学,  Contact page: 46-53

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Papers 【 Display / hide

  • Metal-free thermal organocatalytic pinacol coupling of arylaldehydes using an isonicotinate catalyst with bis(pinacolato)diboron

    Yasui M., Hanaya K., Sugai T., Higashibayashi S.

    RSC Advances (RSC Advances)  11 ( 40 ) 24652 - 24655 2021.07

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    The metal-free thermal organocatalytic pinacol coupling of arylaldehydes has been developed. The intermolecular coupling of arylaldehydes catalyzed byt-butyl isonicotinate with bis(pinacolato)diboron as the co-reducing agent afforded 1,2-diphenylethane-1,2-diols. This reaction was also applicable to the intramolecular coupling of 1,1′-biphenyl-2,2′-dicarbaldehydes to afford 9,10-dihydrophenanthrene-9,10-diols. Various functional groups were tolerated under this coupling condition.

  • Single-molecule electric switching induced by acid-base reaction

    Yoshihara Y., Fujii S., Higashibayashi S., Kiguchi M., Nishino T.

    Chemistry Letters (Chemistry Letters)  50 ( 6 ) 1271 - 1273 2021.06

    ISSN  03667022

     View Summary

    Electric switches are one of the most fundamental electric circuitries. Recent developments in single-molecule techniques allow us to study various electric-switching phenomena on the single-molecule scale. In this study, the switch of the current through a single molecule of a biphenothiazine derivative was investigated using the break junction technique. The biphenothiazine derivative undergoes acid-base reaction-induced electronic modulation due to the reversible structural transformation between a closed shell and an open shell, resulting in a change in the electronic gap and effective tunneling barrier height. We succeeded in controlling the single-molecule electric conductivity of the biphenothiazine derivative wired to two Au electrodes by allowing the reaction to proceed reversibly on the electrode.

  • Chemoenzymatic semisynthesis of caffeic acid β-phenethyl ester, an antioxidative component in propolis, from raw coffee bean extract

    Hashimoto R., Iai H., Fujita R., Hanaya K., Higashibayashi S., Inoue H., Sugai T.

    Bioscience, biotechnology, and biochemistry 85 ( 3 ) 476 - 480 2021.02

    Research paper (scientific journal), Joint Work, Accepted

     View Summary

    © The Author(s) 2020. Published by Oxford University Press on behalf of Japan Society for Bioscience, Biotechnology, and Agrochemistry. Caffeic acid β-phenethyl ester (CAPE), an antioxidative bioactive catechol isolated from propolis, was semisynthesized from chlorogenic acid and related compounds in an extract of raw (unroasted) Robusta coffee (Coffea canephora) beans in 5 steps and a total yield of 31%. Oxidative degradation of the intermediates and target molecule was prevented by alkaline hydrolysis of the chlorogenic acids in the presence of sodium dithionite (Na2S2O4) and deprotection of the catecholic diacetate precursor by Candida antarctica lipase B-mediated transesterification as the final step.

  • Analysis of Interconversion between Atropisomers of Chiral Substituted 9,9’-Bicarbazole

    Kobayashi T., Ishiwari F., Fukushima T., Hanaya K., Sugai T., Higashibayashi S.

    European Journal of Organic Chemistry 2021 ( 3 ) 449 - 451 2021.01

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  1434193X

     View Summary

    © 2020 Wiley-VCH GmbH Interconversion of atropisomers of chiral 3,3’-di-tert-butyl-9,9’-bicarbazole linked by a single N−N bond was analyzed by DFT calculations and experiments. The calculations revealed that the trans transition state has a lower energy for the interconversion than the cis transition state. The lowest transition state of interconversion between natural dixiamycins A and B containing a 9,9’-bicarbazole structure was found to be the trans transition state. The calculations also indicated that degradation through N−N bond cleavage was faster than racemization. Atropisomeric enantiomers of 3,3’-di-tert-butyl-9,9’-bicarbazole were resolved by chiral HPLC for the first time, and then racemization and N−N bond cleavage were investigated by heating experiments, showing that racemization did not take place below the degradation temperature.

  • Semisynthesis of prunetin, a bioactive O-methylated isoflavone from naringenin, by the sequential deacetylation of chalcone intermediates and oxidative rearrangement

    Sugai T., Hanaya K., Higashibayashi S.

    Bioscience, biotechnology, and biochemistry 85 ( 1 ) 143 - 147 2021.01

    Research paper (scientific journal), Joint Work, Accepted

     View Summary

    © The Author(s) 2021. Published by Oxford University Press on behalf of Japan Society for Bioscience, Biotechnology, and Agrochemistry. Prunetin (4',5-dihydroxy-7-methoxyisoflavone) was semisynthesized in 8 steps from readily available naringenin in 26% total yield. The key reaction was chemoenzymatic sequential deacetylation to 6'-acetoxy-2',4″-dihydroxy-4'-methoxychalcone, the in situ-formed precursor for thallium(III) nitrate-mediated oxidative rearrangement.

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

Reviews, Commentaries, etc. 【 Display / hide

  • Recent examples of the use of biocatalysts with high accessibility and availability in natural product synthesis

    Takeshi Sugai, Shuhei Higashibayashi, Kengo Hanaya

    Tetrahedron  74   3469 - 3487 2018

    Introduction and explanation (scientific journal), Joint Work

  • Synthesis of Sumanene and Related Buckybowls

    huhei Higashibayashi, Hidehiro Sakurai

    Chemistry Letters 40   122 - 128 2011

    Introduction and explanation (scientific journal), Joint Work

  • おわん型共役炭素化合物バッキーボウルの合成


    有機合成化学協会誌 67   38 - 50 2009

    Introduction and explanation (scientific journal), Single Work

Presentations 【 Display / hide

  • 超原子価ヨウ素酸化剤を用いた位置選択的水酸化と 1,2-転位による置換カテコール合成法の開拓

    橋本理一, 花屋賢悟, 須貝威, 東林修平

    第48回有機典型元素化学討論会, 2021.12, Poster (general)

  • ピリジンージボロン系を利用したメタルフリーピナコールカップリングの開拓

    安井将満, 花屋賢悟, 須貝威, 東林修平

    第48回有機典型元素化学討論会, 2021.12, Poster (general)

  • 超原子価ヨウ素酸化剤を用いたフェノールとアルケンの酸化的芳香族求核置換反応の開拓

    出口裕己, 花屋賢悟, 須貝威, 東林修平

    第48回有機典型元素化学討論会, 2021.12, Poster (general)

  • ピリジン触媒とジボロンを用いた芳香族アルデヒド類のメタルフリーピナコールカップリングの開拓

    安井将満, 花屋賢悟, 須貝威, 東林修平

    第50回複素環化学討論会, 2021.10, Poster (general)

  • シンビオイミンの全合成を志向した、ヒドロキノリン骨格の官能基選択性非依存的構築法の開拓

    藤田理愛, 花屋賢悟, 須貝威, 東林修平

    第50回複素環化学討論会, 2021.10, Poster (general)

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

  • 酸化的芳香族-アルケンカップリングの開発と展開


    MEXT,JSPS, Grant-in-Aid for Scientific Research, 東林 修平, Grant-in-Aid for Scientific Research (C), Principal Investigator

  • ジグザグ型ヘテロカーボンナノベルトの合成


    MEXT,JSPS, Grant-in-Aid for Scientific Research, 東林 修平, Grant-in-Aid for Challenging Research (Exploratory) , Principal Investigator

Awards 【 Display / hide

  • 有機合成化学奨励賞

    2012, おわん型π共役分子バッキーボウルの合成

  • 日本化学会第90春季年会「若い世代の特別講演会」

    2010, C3対称バッキーボウルの液相合成法の開発

  • 日本化学会第87春季年会優秀講演賞

    2007, キラルバッキーボウルの合成研究

  • 天然物化学談話会奨励賞

    2005, 非環状天然有機化合物の立体配置決定法Universal NMR Databaseの開発


Courses Taught 【 Display / hide











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Memberships in Academic Societies 【 Display / hide

  • 日本薬学会

  • 日本化学会

  • 有機合成化学協会

  • 基礎有機化学会