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

Licenses and Qualifications 【 Display / hide

  • 甲種危険物取扱者, 2004.08

 

Research Areas 【 Display / hide

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

  • Life Science / Bioorganic 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

  • 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.

  • Selective modification of tryptophan in polypeptides via C-N coupling with azoles using in situ-generated iodine-based oxidants in aqueous media

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

    Chemical Communications (Chemical Communications)  59 ( 87 ) 13026 - 13029 2023.10

    Research paper (scientific journal), Accepted,  ISSN  13597345

     View Summary

    This study demonstrates the C-N coupling of tryptophan with azoles, promoted by an in situ-generated iodine-based oxidant. The protocol was successfully applied to the selective modification of tryptophan in nonprotected polypeptide bearing oxidatively sensitive residues in acidic aqueous media. The present method allows the attachment of reactive handles to polypeptides and the peptide stapling.

  • Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway

    Kobayashi T., Ishiwari F., Fukushima T., Nojima Y., Hasegawa M., Mazaki Y., Hanaya K., Sugai T., Higashibayashi S.

    Chemistry - A European Journal (Chemistry - A European Journal)  29 ( 43 )  2023.08

    Research paper (scientific journal), Accepted,  ISSN  09476539

     View Summary

    1,1’,10,10’-Biphenothiazine and its S,S,S’,S’-tetroxide are diaza[5]helicenes with N−N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N−N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N−N bond by modification of S to SO2 at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1’,10,10’-Biphenothiazine S,S,S’,S’-tetroxide was highly resistant to acid-mediated N−N bond breaking and racemization under acidic conditions.

  • Transition-Metal-Free β-Selective C-Glycosylation of β-Glycosyl Boronates via Stereoretentive 1,2-Migration

    Yasutomi H., Takeda D., Yoritate M., Higashibayashi S., Sugai T., Hirai G.

    Synlett (Synlett)  34 ( 4 ) 347 - 352 2023.03

    Research paper (scientific journal), Accepted,  ISSN  09365214

     View Summary

    C-Glycoside analogues of native glycans are useful molecular tools for medicinal chemistry and chemical biology due to their resistance to cellular glycoside hydrolases. We previously reported an α-selective direct C-glycosylation of 2-deoxy-β-glycosyl boronate through a Ni/photoredox-catalyzed stereoinvertive cross-coupling reaction. Here we report a complementary stereoretentive synthetic method for the preparation of β-C-glycosides from a similar boronate precursor through the addition of a C(sp2) anion followed by 1,2-migration of the glycosyl donor.

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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

    Article, review, commentary, editorial, etc. (scientific journal), Joint Work

  • Synthesis of Sumanene and Related Buckybowls

    huhei Higashibayashi, Hidehiro Sakurai

    Chemistry Letters 40   122 - 128 2011

    Article, review, commentary, editorial, etc. (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

    東林修平

    有機合成化学協会誌 67   38 - 50 2009

    Article, review, commentary, editorial, etc. (scientific journal), Single Work

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

    HIGASHIBAYASHI Shuhei

    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

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

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

    2023

  • SEMINAR: (ORGANIC AND BIOCATALYTIC CHEMISTRY)

    2023

  • RESEARCH FOR BACHELOR'S THESIS 1

    2023

  • PHARMACEUTICAL-ENGLISH SEMINAR

    2023

  • PHARMACEUTICAL CHEMISTRY AND MATERIALS

    2023

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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