Higashibayashi, Shuhei

写真a

Affiliation

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

Position

Associate Professor
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Licenses and Qualifications 【 Display / hide 】

  • 甲種危険物取扱者, 2004.08

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Research Areas 【 Display / hide 】

  • Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

  • Life Science / Bioorganic chemistry

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Books 【 Display / hide 】

  • 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

  • 使える！有機合成反応241実践ガイド

    櫻井英博, 東林修平, 他（丸岡啓二, 野崎京子, 石井康敬, 大寺純蔵, 富岡清編著）, 化学同人, 2010

    Contact page： 86-87

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Papers 【 Display / hide 】

  • Development of Catalytic Reactions Using Bis(pinacolato)diboron and Their Applications to Syntheses of Pharmaceuticals and Luminescent Dyes

    Shuhei Higashibayashi

    Journal of Synthetic Organic Chemistry 82 ( 11 ) 1052 - 1062 2024.11

    Research paper (scientific journal), Single Work, Lead author, Corresponding author, Accepted,  ISSN  00379980

    　View Summary

    We have developed three catalytic reactions involving borylation and C—C bond formation using bis(pinacolato)diboron (B2pin2), and have extended their use to the synthesis of pharmaceuticals and luminescent dyes. In addition, we have also elucidated the photophysical properties of those dyes. The first reaction is a Cu—catalyzed stereoselective borylation of glycosyl bromide to β—glycosyl trifluoroborates, which has been further expanded to synthesize aryl β—C—glycosides via Pd—catalyzed stereospecific cross—coupling with aryl bromides. These methods were applied to the stereospecific synthesis of the SGLT2 inhibitor, canagliflozin. The second reaction involves the copper—catalyzed borylation of acyl chlorides to form acyl trifluoroborates, which have further been applied to the synthesis of fluorescent C,N—chelated 2,2—difluoro—1,4—diazaboroles via condensation with various amino—heterocycles. The third reaction is an organocatalytic pinacol coupling of aryl aldehydes using B2pin2 as a reductant and a substituted pyridine catalyst. The resulting diols were converted to various substituted benzils, revealing the luminescent properties such as phosphorescence, fluorescence, and self—recovering phosphorescence—to—phosphorescence mechanochromism. These studies demonstrated the usefulness of the developed methods for producing pharmaceuticals, pharmaceutical candidates and novel materials, as well as making possible the investigation of the products physical properties.

  • Synthesis and property of 2,2-difluoro-1,4-diazaborole

    Nakahara M., Wada Y., Kawano M., Hanaya K., Sugai T., Higashibayashi S.

    Chemistry Letters (Chemistry Letters)  53 ( 5 ) upae069 2024.05

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  03667022

    　View Summary

    The synthesis of 2,2-difluoro-1,4-diazaboroles was achieved through the condensation of aliphatic acyltrifluoroborates and amino-N-heteroarenes under acidic conditions. Various N-heteroarenes, including pyridine, pyrimidine, pyridazine, thiazole, and isoquinoline, were successfully employed in the reaction. Among the synthesized 2,2-difluoro-1,4-diazaboroles, the one with an isoquinoline structure exhibited the most intense light blue emission.

  • Utilization of Lipase-Catalyzed Acetylation and Deacetylation in the Synthesis of a Natural Product with a Hydroquinone Skeleton

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

    Asian Journal of Organic Chemistry    e202400303 2024

    Research paper (scientific journal), Joint Work, Accepted

    　View Summary

    Elaborated conditions for lipase-catalyzed preferential monoacetylation enabled the large-scale preparation of hydroquinone monoacetate. This product was then applied to the synthesis of tournefolin B, a highly oxygenated prenylated hydroquinone of plant origin (Tournefortia sarmentosa Lam.). During the course of the synthetic transformations, lipase-catalyzed deacetylation under mild conditions was demonstrated.

  • Unified short syntheses of oxygenated tricyclic aromatic diterpenes by radical cyclization with a photoredox catalyst

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

    Communications Chemistry (Communications Chemistry)  6 ( 1 )  2023.12

    Research paper (scientific journal), Accepted

    　View Summary

    The biomimetic two-phase strategy employing polyene cyclization and subsequent oxidation/substitution is an effective approach for divergent syntheses of [6-6-6]-tricyclic diterpenes. However, this strategy requires lengthy sequences for syntheses of oxygenated tricyclic aromatic abietane/podocarpane diterpenes owing to the many linear oxidation/substitution steps after cyclization. Here, we present a new synthetic route based on a convergent reverse two-phase strategy employing a reverse radical cyclization approach, which enabled the unified short syntheses of four aromatic abietane/podocarpane diterpenes and the divergent short syntheses of other related diterpenes. Oxygenated and substituted precursors for cyclization were convergently prepared through Friedel-Crafts acylation and rhodium-catalyzed site-selective iodination. Radical redox cyclization using an iridium photoredox catalyst involving neophyl rearrangement furnished the thermodynamically favored 6-membered ring preferentially. (±)-5,6-Dehydrosugiol, salvinolone, crossogumerin A, and Δ5-nimbidiol were synthesized in only 8 steps. An oxygenated cyclized intermediate was also useful for divergent derivatization to sugiol, ferruginol, saprorthoquinone, cryptomeriololide, and salvinolone.

  • Synthesis and luminescence properties of substituted benzils

    Yasui M., Fujihara T., Ohtsu H., Wada Y., Shimada T., Zhu Y., Kawano M., Hanaya K., Sugai T., Higashibayashi S.

    Communications Chemistry (Communications Chemistry)  6 ( 1 )  2023.12

    Research paper (scientific journal), Accepted

    　View Summary

    Photophysical properties of benzil (1,2-diphenylethane-1,2-dione) and its derivatives in the crystal state have recently attracted much attention. However, the study of substituted benzils has mostly been limited to para-substituted derivatives, which did not induce a significant effect on the emission wavelength compared to pristine benzil. The effects of ortho- and meta-substituents on the photophysical properties in the crystal state have not been investigated so far. Our recently developed organocatalytic pinacol coupling of substituted benzaldehydes allowed us to prepare various ortho-, meta-, and para-substituted benzil derivatives and to investigate their luminescence properties. Ortho- and meta-substituents affected the electronic states of benzils in the crystal state, resulting in differences in their luminescence properties. The luminescence wavelength and type, i.e., phosphorescence or fluorescence, were altered by these substituents. Fast self-recovering phosphorescence-to-phosphorescence mechanochromism by the para-CF3 substituent at room temperature was also discovered.

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

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Reviews, Commentaries, etc. 【 Display / hide 】

  • Synthesis and property of three-dimensional curved heterocyclic π-electron molecules with embedded nitrogen atoms

    Shuhei Higashibayashi

    J. Synth. Org. Chem. Jpn.  77   1209 - 1221 2019

    Single Work

  • 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

  • Enantioselective synthesis of chiral buckybowl and chiral azabuckybowl

    Shuhei Higashibayashi

    J. Synth. Org. Chem. Jpn. 72   26 - 38 2014

  • 2013年の化学: 注目の論文「カーボンナノチューブの三叉路」

    東林修平

    月刊化学 68   59 - 60 2013

  • 炭素・窒素原子でできた「おわん分子」を合成

    東林修平

    セラミックス 47   806 - 806 2012

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Presentations 【 Display / hide 】

  • アシルホウ素化合物の新規触媒的合成と蛍光分子への展開

    中原正貴, 倉林一樹, 花屋賢悟, 須貝威, 東林修平

    第85回有機合成化学協会関東支部シンポジウム, 

    2023.11
    , 

    Oral presentation (general)

  • Stereospecific synthesis of aryl C-glycosides

    Shuhei Higashibayashi

    The 16th Keio LCC-Yonsei CBMH Joint Symposium (Tokyo) , 

    2023.11
    , 

    Oral presentation (invited, special)

  • グリコシルホウ酸塩を用いたアリールC-グリコシド合成法の開発

    東林修平

    第67回日本薬学会関東支部大会, 

    2023.09
    , 

    Oral presentation (invited, special)

  • 収束的な逆二段階法による三環性ジテルペン類の合成

    橋本理一, 花屋賢悟, 東林修平, 須貝威

    第65回天然有機化合物討論会, 

    2023.09
    , 

    Poster presentation

  • 収束的な逆二段階法による三環性ジテルペン類の合成

    橋本理一, 花屋賢悟, 東林修平, 須貝威

    第122回有機合成シンポジウム, 

    2023.07
    , 

    Oral presentation (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

    2020.04
    -
    2023.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, 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

    2017.06
    -
    2019.03

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

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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

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Courses Taught 【 Display / hide 】

  • STUDY OF MAJOR FIELD (ADVANCED MOLECULAR CHEMISTRY)

    2024

  • SEMINAR (ADVANCED MOLECULAR CHEMISTRY)

    2024

  • RESEARCH FOR BACHELOR'S THESIS 1

    2024

  • PHARMACEUTICAL-ENGLISH SEMINAR

    2024

  • PHARMACEUTICAL CHEMISTRY AND MATERIALS

    2024

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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

    　
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