Sugai, Takeshi

写真a

Affiliation

Faculty of Pharmacy 有機薬化学講座 （Mita）

Position

Professor Emeritus

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Career 【 Display / hide 】

  • 1984.04
    -
    1988.03

    東京大学農学部文部教官助手

  • 1988.04
    -
    1993.03

    慶應義塾大学（理工学部）、助手

  • 1991.08
    -
    1992.09

    Research Associate, The Scripps Research Institute

  • 1993.04
    -
    1997.03

    慶應義塾大学（理工学部）、専任講師

  • 1994.10
    -
    1995.03

    茨城大学大学院（生物化学工学特別講義）、非常勤講師

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Academic Background 【 Display / hide 】

  • 1981.03

    The University of Tokyo, Faculty of Agriculture, 農芸化学科

    University, Graduated

  • 1983.03

    The University of Tokyo, Graduate School, Division of Agricultural Science, 農芸化学専門課程

    Graduate School, Completed, Master's course

  • 1984.03

    The University of Tokyo, Graduate School, Division of Agricultural Science, 農芸化学専門課程

    Graduate School, Withdrawal before completion, Doctoral course

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Academic Degrees 【 Display / hide 】

  • 農学　, The University of Tokyo, 1987.06

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Research Areas 【 Display / hide 】

  • Manufacturing Technology (Mechanical Engineering, Electrical and Electronic Engineering, Chemical Engineering) / Catalyst and resource chemical process (Catalyst and Chemical Process)

  • Manufacturing Technology (Mechanical Engineering, Electrical and Electronic Engineering, Chemical Engineering) / Biofunction and bioprocess engineering (Bioengineering)

  • Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry (Organic Chemistry)

  • Nanotechnology/Materials / Synthetic organic chemistry (Synthetic Chemistry)

  • Life Science / Bioorganic chemistry (Organic Chemistry)

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Books 【 Display / hide 】

  • “Future Directions in Biocatalysis (Second Edition)”

    R. Tsunekawa, K. Hanaya, M. Shoji, T. Sugai, T. Matsuda, ed., Elsevier, 2017.08

    Scope: 279–295

  • “Comprehensive Organic Synthesis II (Second Edition) Volume 2: Additions to C–X Π-Bonds, Part 2”

    T. Sugai, K. Fushuku, P. Knochel, G. A. Molander, eds., Elsevier, 2014.01

    Scope: 512–522

  • Practical Methods for Biocatalysis and Biotransformations

    T. Sugai, A. Fujino, H. Yamaguchi, M. Ikunaka, J. Whittal, P. W. Sutton, eds., Wiley, 2009.12

    Scope: 190-198

  • Glycoscience: Chemistry and Chemical Biology

    T. Sugai, T. Kajimoto, Springer-Verlag GmbH, Berlin Heidelberg New York (B. O. Fraser-Reid, K. Tatsuta, J. Thiem eds.), 2001.12

    Scope: 907-1021

    　View Summary

    単糖類の化学・酵素合成における最近の進歩について解説した。

  • Enzymes in Nonaqueous Solvents; Methods and Protocols, Methods in Biotechnology

    Springer, 2001.10

    Scope: 401-416

    　View Summary

    界面バイオリアクターを用いる、微生物物質変換反応について著者らの成果を中心に解説した。

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Papers 【 Display / hide 】

  • 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 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.

  • 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 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.

  • 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 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 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.

  • Intramolecular cyclization of m-homoprenylphenols through oxidative nucleophilic aromatic substitution

    Deguchi H., Hanaya K., Sugai T., Higashibayashi S.

    Chemical Communications 59 （ 6 ） 748 - 751 2022.12

    Research paper (scientific journal), Accepted

    　View Summary

    We developed an intramolecular cyclization of m-homoprenylphenols and related m-prenylphenols to bicyclic skeletons by hypervalent iodine reagents through an oxidative nucleophilic aromatic substitution using the prenyl group as a carbon nucleophile. The reaction was applicable for the syntheses of 5/6-, 6/6-, and 7/6-fused ring systems.

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

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Presentations 【 Display / hide 】

  • The development of the synthetic routes utilizing the selectivity in enzyme catalysis

    T. Sugai

    Pacificem2021 (Online) , 

    2021.12
    , 

    Oral presentation (invited, special), Pacifichem

    　View Summary

    In the organic process chemistries, the integrated use of
    chemo- (organic synthesis) enzymatic (biotechnology) transformation
    approach takes advantages over individual procedures, towards the best
    solution to make the design and diagram for target compounds. In this talk,
    we focus upon the use of lipases, which are developed for food
    manufacturing and detergent industries, and cheaply commercially
    available. Lipases work starting by the nucleophilic attack of serine hydroxy
    groups involved in their active sites, and the subsequent decomposition of
    enzyme-substrate complexes provide products and regenerate active
    enzymes. By the attack with alcohols for the latter step, lipases, especially
    in immobilized forms, exhibit the catalytic activities of transesterification in
    organic solvents. Those activities were demonstrated for deprotection of
    phenolic esters and kinetic resolution of enantiomers [1]. The rate of lipasecatalyzed
    transesterification on polyphenolic substrates are affected by the
    neighboring steric hindrance [2]. When flavonoid acetates and their
    glycosylated forms were submitted to lipase-catalyzed transestericiation
    conditions, deacetylation preferentially occur at C-4‘ position, the least
    hindered phenolic acetates [3-5]. When severely hindered
    naphthohydroquinone diacetate with both ortho- and peri- substituents,
    diverse site selectivity was observed depending upon the sort of lipases [6].
    Lipase-triggered aldol reaction is also presented. Indoxyl acetate was a
    good substrate for the deacetylation with lipases. The syntheses of
    indirubin and 6-bromoindirubin were achieved via the aldol condensation
    between isatins and an indoxyl anion generated by lipase-catalyzed
    reaction with triethylamine, under anhydrous and anaerobic conditions as
    the key step [7]

  • Enzyme-assisted syntheses of bioactive compounds, originated from Scripps days

    T. Sugai

    2019 Scripps Korea Society Symposium (Yonsei University, Seoul, Korea) , 

    2019.08
    , 

    Oral presentation (invited, special)

  • New Entries for Transformation of Carbohydrates towards the Synthesis of Bioactive Compounds

    T. Sugai

    2018 Frontiers in Chemical Biology (Hotel Royal Chiao Hsi, Yilan County, Taiwan) , 

    2018.08
    , 

    Oral presentation (invited, special)

  • Enzyme-catalyzed Asymmetric Reduction of Cyclic Ketoesters and Application to Natural Product Synthesis

    T. Sugai, K. Kuwata, R. Tsunekawa, R. Fujita

    The 13th Yonsei CBMH-Keio LCC Joint Symposium (Yonsei University, Seoul, Korea) , 

    2017.10
    , 

    Oral presentation (invited, special)

  • The Complementary and Integrated Chemo-enzymatic Processes for Fine Chemical Syntheses (Invited Lecture)

    T. Sugai, Y. Yamashita, Y. Niitsu, M. Hamada, C. Hiraoka, T. Higashi, M. Shoji

    The 14th Asia Pacific Confederation of Chemical Engineering (Singapore, Singapore) , 

    2012.02
    , 

    Oral presentation (invited, special)

    　View Summary

    カルバ糖およびDHMEQを題材に、リパーゼによる位置および立体選択的変換について最新の成果を報告した。

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

  • 位置・立体選択的反応を鍵段階とする生物活性物質の合成研究

    2019.04
    -
    2022.03

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

  • Efficient organic synthesis utilizing microbial enzyme catalysts

    2014.04
    -
    2017.03

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

    　View Summary

    Complementary and synergistic utilization of enzyme-catalyzed reactions and chemical transformation was studied, toward the efficient synthesis of complex target molecules involving valuable natural and unnatural products. The achievements are shown below. Lipase-catalyzed transesterification proceeded with specific site-selectivity contrasting to chemical transformations, and the syntheses of selinone and astringin, artepillin C became successful. It was revealed that the transesterification under non-aqueous conditions was advantageous for the substrates which are labile to water and/or prone to protonation under aqueous conditions. The preparation of highly enantiomerically pure (R)-3-hydroxy-N-methylpiperidine by the lipase-catalyzed kinetic resolution of corresponding racemate was established. The synthesis of enantiomers of NMB carboxylic acid was also successful, by discriminating he stereochemistry of remote chiral center in a primary acetate, as the key step.

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Awards 【 Display / hide 】

  • 化学教育賞

    須貝 威, 2021.03, 日本化学会, 高校生から大学生までを惹きつける生物有機化学と実験

    Type of Award： Award from Japanese society, conference, symposium, etc.

  • 有機合成化学協会賞

    須貝 威, 2020.02, 有機合成化学協会, 酵素触媒の選択性を活用した有用物質合成法の開拓

    Type of Award： Award from Japanese society, conference, symposium, etc.

  • Presidential 2000 Green Chemistry Challenge Award, as a co-recipient of the honoring C.-H. Wong

    Takeshi Sugai, 2000.06, Department of Environmental Protection, USA,, Enzymes in Large-scale Organic Synthesis

    Type of Award： Other

  • 農芸化学奨励賞

    須貝 威, 1994.04, 日本農芸化学会, 生体触媒を利用する不斉合成と物質生産への応用

    Type of Award： Award from Japanese society, conference, symposium, etc.

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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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Social Activities 【 Display / hide 】

  • 化学情報協会

    2001.04
    -
    2002.03
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Memberships in Academic Societies 【 Display / hide 】

  • Current Organic Synthesis, 

    2003.01
    -
    Present

  • Mini-Reviews in Organic Chemistry, 

    2003.01
    -
    Present

  • 日本化学会, 

    2004.04
    -
    Present

  • 日本農芸化学会, 

    2001.03
    -
    Present

  • 日本糖質学会, 

    1999.04
    -
    Present

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Committee Experiences 【 Display / hide 】

  • 2003.01
    -
    Present

    Editorial Advisory Board, Current Organic Synthesis

  • 2003.01
    -
    Present

    Editorial Advisory Board, Mini-Reviews in Organic Chemistry

  • 2004.04
    -
    Present

    化学教育協議会大学入試21WG委員, 日本化学会

  • 2001.03
    -
    Present

    日本農芸化学会誌編集幹事, 日本農芸化学会

  • 1999.04
    -
    Present

    評議員, 日本糖質学会

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