東林 修平 (ヒガシバヤシ シュウヘイ)

Higashibayashi, Shuhei

写真a

所属(所属キャンパス)

薬学部 薬科学科 有機薬化学講座 (芝共立)

職名

准教授

免許・資格 【 表示 / 非表示

  • 甲種危険物取扱者, 2004年08月

 

研究分野 【 表示 / 非表示

  • ナノテク・材料 / 構造有機化学、物理有機化学

  • ライフサイエンス / 生物有機化学

 

著書 【 表示 / 非表示

  • Control of inversion kinetics of bowl-shaped aromatic compounds

    Higashibayashi S., Kinetic Control in Synthesis and Self-Assembly, 2018年01月

     概要を見る

    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年

    担当範囲: Chapter 4, “Control of Inversion Kinetics of Bowl-Shaped Aromatic Compounds”,  担当ページ: 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年

    担当範囲: Chapter 6, "Chiral Sumanene, Triazasumanene, and Related Buckybowls",  担当ページ: 91-106

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

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

    担当範囲: Chapter 3, "Growing Buckybowl Chemistry",  担当ページ: 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年

    担当範囲: 第1章 精密合成が拓くπ電子科学,  担当ページ: 46-53

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論文 【 表示 / 非表示

  • 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年12月

    研究論文(学術雑誌), 査読有り

     概要を見る

    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年12月

    研究論文(学術雑誌), 査読有り

     概要を見る

    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年10月

    研究論文(学術雑誌), 査読有り,  ISSN  13597345

     概要を見る

    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年08月

    研究論文(学術雑誌), 査読有り,  ISSN  09476539

     概要を見る

    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年03月

    研究論文(学術雑誌), 査読有り,  ISSN  09365214

     概要を見る

    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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総説・解説等 【 表示 / 非表示

  • 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年

    記事・総説・解説・論説等(学術雑誌), 共著

  • Synthesis of Sumanene and Related Buckybowls

    huhei Higashibayashi, Hidehiro Sakurai

    Chemistry Letters 40   122 - 128 2011年

    記事・総説・解説・論説等(学術雑誌), 共著

  • 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年

    記事・総説・解説・論説等(学術雑誌), 単著

研究発表 【 表示 / 非表示

  • 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年11月

    口頭発表(一般)

  • Stereospecific synthesis of aryl C-glycosides

    HIGASHIBAYASHI Shuhei

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

    2023年11月

    口頭発表(招待・特別)

  • 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年09月

    口頭発表(招待・特別)

  • 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年09月

    ポスター発表

  • 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年07月

    口頭発表(一般)

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競争的研究費の研究課題 【 表示 / 非表示

  • 酸化的芳香族-アルケンカップリングの開発と展開

    2020年04月
    -
    2023年03月

    文部科学省・日本学術振興会, 科学研究費助成事業, 東林 修平, 基盤研究(C), 補助金,  研究代表者

  • ジグザグ型ヘテロカーボンナノベルトの合成

    2017年06月
    -
    2019年03月

    文部科学省・日本学術振興会, 科学研究費助成事業, 東林 修平, 挑戦的研究(萌芽), 補助金,  研究代表者

受賞 【 表示 / 非表示

  • 有機合成化学奨励賞

    2012年, 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年, 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年, 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年, 非環状天然有機化合物の立体配置決定法Universal NMR Databaseの開発

 

担当授業科目 【 表示 / 非表示

  • 課題研究(有機薬化学)

    2023年度

  • 演習(有機薬化学)

    2023年度

  • 卒業研究1(薬学科)

    2023年度

  • 英語演習(薬学科)

    2023年度

  • 物質機能化学特論

    2023年度

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所属学協会 【 表示 / 非表示

  • 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