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Synthesis of Biologically Active Oligosaccharide Using Anomerization Reaction via Endocyclic Cleavage Reaction

Research Project

Project/Area Number 24590041
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionInstitute of Physical and Chemical Research

Principal Investigator

Manabe Shino  国立研究開発法人理化学研究所, 伊藤細胞制御化学研究室, 専任研究員 (60300901)

Project Period (FY) 2012-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2013: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2012: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords糖 / ピラノシド / 異性化 / エンド開裂反応 / 1,2-cis アミノグリコシド / 置換基効果 / 糖鎖 / アミノ糖 / 1,2-cis グリコシド / エンド開裂 / アミノグリコシド / 保護基 / ヘパロサン
Outline of Final Research Achievements

The bond between anomeric position and external oxygen is cleaved in endocyclic cleavage reaction. Endocyclic cleavage reaction is rare in glycoscience. We found endocyclic cleavage reaction is promoted by protection of amino group at 2-amino group and 3-hydroxy group by cyclic carbamate group. Clear evidence of endocyclic cleavage reaction was demonstrated by capturing acyclic cation by reduction and intramolecular Friedel-Crafts reaction. Investigation on substituent effect reveals Ac group makes complete anomerization in various substrates. By using endocyclic cleavage reaction, existing multiple stereochemistries at anomeric position can be changed to α-isomer, which is difficult to be created by conventional glycosylation reaction. Novel α-linked chitosan oligomer was synthesized from β-chitosan in one-step.

Report

(5 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Research-status Report
  • 2013 Research-status Report
  • 2012 Research-status Report
  • Research Products

    (33 results)

All 2015 2014 2013 2012 Other

All Int'l Joint Research (1 results) Journal Article (9 results) (of which Peer Reviewed: 8 results,  Acknowledgement Compliant: 1 results) Presentation (18 results) (of which Int'l Joint Research: 4 results,  Invited: 3 results) Book (3 results) Patent(Industrial Property Rights) (2 results) (of which Overseas: 1 results)

  • [Int'l Joint Research] Zurich University/Swiss Federal Institute of Technology/IBM Research Zurich(スイス)

    • Related Report
      2015 Annual Research Report
  • [Journal Article] Significant substituent effect on the anomerization of pyranosides: mechanism of anomerization and synthesis of a 1,2-cis glucosamine oligomer from the 1,2-trans anomer2014

    • Author(s)
      Shino Manabe, Hiroko Satoh, Jürg Hutter, Hans Peter Lüthi, Teodoro Laino, Yukishige Ito,
    • Journal Title

      Chem. Eur. J

      Volume: 20 Issue: 1 Pages: 124-132

    • DOI

      10.1002/chem.201303474

    • Related Report
      2014 Research-status Report 2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pyranosides with 2,3-trans Carbamate Groups: Exocyclic or Endocyclic Cleavage Reaction2014

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Journal Title

      The Chemical Record

      Volume: 14 Issue: 3 Pages: 502-515

    • DOI

      10.1002/tcr.201402004

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Sulfonylcarbamate as a Versatile and Unique Hydroxy-Protecting Group: Protecting Group Stable under Severe Conditions and Labile under Mild Conditions2013

    • Author(s)
      Shino Manabe, Masanori Yamaguchi, Yukishige Ito
    • Journal Title

      Chem. Comm

      Volume: 49 Issue: 75 Pages: 8332-8334

    • DOI

      10.1039/c3cc43968b

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Hafnium(IV) Tetratriflate in Selective Reductive Carbohydrate Benzylidene Acetal Opening Reaction and Direct Silylation Reaction2013

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Journal Title

      Tetrahedron Lett.

      Volume: 54 Issue: 50 Pages: 6838-6840

    • DOI

      10.1016/j.tetlet.2013.10.011

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Glycosylation Reaction: Relationship between Conformation and Reactivity, Investigation From Experimental and Computational Chemistry2013

    • Author(s)
      Hiroko Satoh, Shino Manabe
    • Journal Title

      Chem. Soc. Rev.

      Volume: 42 Pages: 4297-4309

    • Related Report
      2013 Research-status Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] 2,3-transカーバメート基を持つ糖構造の特異な反応性:糖化学におけるエンド開裂反応の再発見2013

    • Author(s)
      眞鍋史乃、佐藤寛子
    • Journal Title

      有機合成化学協会誌

      Volume: 71 Pages: 616-624

    • NAID

      130003373306

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Cremer-Popleモデル2013

    • Author(s)
      眞鍋史乃
    • Journal Title

      有機合成化学協会誌

      Volume: 71 Pages: 643-643

    • Related Report
      2013 Research-status Report
  • [Journal Article] Hafnium(IV) Tetratriflate as a Glycosyl Fluoride Activation Reagent2013

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Journal Title

      Journal of Organic Chemistry

      Volume: 78 Issue: 9 Pages: 4568-4572

    • DOI

      10.1021/jo400282x

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] 2,3-transカーバメート基を持つ糖構造の特異な反応性:糖化学におけるエンド開裂反応の再発見2013

    • Author(s)
      眞鍋 史乃、佐藤 寛子
    • Journal Title

      有機合成化学協会誌

      Volume: 71

    • NAID

      130003373306

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Presentation] Control of stereochemistry at anomeric centers via acyclic cation formation: The endocyclic cleavage reaction2015

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Organizer
      THE INTERNATIONAL CHEMICAL CONGRESS OF PACIFIC BASIN SOCIETIES 2015 (PACIFICHEM2015)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-18
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Sulfonylcarbamate as a unique hydroxy protecting group: Protecting group stable under severe conditions yet labile under mild conditions2015

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Organizer
      THE INTERNATIONAL CHEMICAL CONGRESS OF PACIFIC BASIN SOCIETIES 2015 (PACIFICHEM2015)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Reinvestigation of Glycosyl Bond Cleavage2015

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Organizer
      Gordon Research Conference, Cellulosomes, Cellulases & Other Carbohydrate Modifying Enzymes
    • Place of Presentation
      Andover, USA
    • Year and Date
      2015-08-06
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 非環状カチオンを経由するアノマー位立体制御法:エンド開裂反応とその合成的有用性2015

    • Author(s)
      眞鍋史乃
    • Organizer
      日本糖質学会第34回会
    • Place of Presentation
      東京大学、東京
    • Year and Date
      2015-08-01
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] Pyranosides with 2,3-trans Carbamate Group: Exocyclic Cleavage or Endocyclic Cleavage2015

    • Author(s)
      Shino Manabe
    • Organizer
      Gordon Research Conference
    • Place of Presentation
      West Dover, USA
    • Year and Date
      2015-06-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 異性化反応による mycothiol 合成研究2014

    • Author(s)
      眞鍋史乃、伊藤幸成
    • Organizer
      第33回日本糖質学会年会
    • Place of Presentation
      名古屋大学豊田講堂
    • Year and Date
      2014-08-10 – 2014-08-12
    • Related Report
      2014 Research-status Report
  • [Presentation] 温和な塩基性条件において除去可能、かつ、強い塩基性条件において安定である保護基2014

    • Author(s)
      眞鍋史乃、伊藤幸成
    • Organizer
      日本プロセス学会、2014 サマーシンポジウム
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2014-07-31 – 2014-08-01
    • Related Report
      2014 Research-status Report
  • [Presentation] 異性化反応による1,2-cis アミノグリコシドの合成2014

    • Author(s)
      眞鍋史乃、伊藤幸成
    • Organizer
      第94回日本化学会年会
    • Place of Presentation
      名古屋、名古屋大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 鎖状カチオンを経由する1,2-cisグルコサミンオリゴマーの合成2013

    • Author(s)
      眞鍋史乃、伊藤幸成
    • Organizer
      第32回日本糖質学会
    • Place of Presentation
      大阪、大阪国際交流センター
    • Related Report
      2013 Research-status Report
  • [Presentation] 既存グリコシドの異性化反応を利用した新規糖鎖合成2013

    • Author(s)
      眞鍋史乃、伊藤幸成
    • Organizer
      日本プロセス化学会2013サマーシンポジウム
    • Place of Presentation
      筑波、つくば国際会議場
    • Related Report
      2013 Research-status Report
  • [Presentation] Synthesis of α-glycosamine oligomer from β-glucosamine oligomer by endocyclic cleavage reaction2013

    • Author(s)
      Shino Manabe, Yukishige Ito
    • Organizer
      10th Asia-Pacific Chitin&Chitosan Symposium
    • Place of Presentation
      Yonago, Yonago convention center, Bigship
    • Related Report
      2013 Research-status Report
  • [Presentation] 鎖状カチオンを経由したピラノシドの異性化反応による1,2-cis アミノグリコシドオリゴマーの合成2013

    • Author(s)
      眞鍋史乃、佐藤寛子、Jurg Hutter, Hans Peter Luthi, Teodoro Laino, 伊藤幸成
    • Organizer
      第39回反応と合成の進歩シンポジウム
    • Place of Presentation
      福岡、九州大学百年記念講堂
    • Related Report
      2013 Research-status Report
  • [Presentation] ピラノシドのエンド開裂反応と置換基効果2013

    • Author(s)
      眞鍋史乃、石井一之、越野広雪、伊藤幸成
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      パシフィコ横浜、横浜
    • Related Report
      2012 Research-status Report
  • [Presentation] グリコシドのC-O結合開裂反応:2,3-transに環状保護基をもつグリコシドにおけるエンド開裂反応の主要支配因子の解明と反応性予測2012

    • Author(s)
      佐藤寛子,眞鍋史乃,伊藤幸成,Hans P. Luethi, Teodoro Laino, Juerg Hutter
    • Organizer
      第101回有機合成化学協会シンポジウム
    • Place of Presentation
      慶応大学薬学部、東京
    • Related Report
      2012 Research-status Report
  • [Presentation] エンド開裂反応を利用した1,2-cis アミノグリコシドアノマー位立体制御 と新規糖鎖合成2012

    • Author(s)
      眞鍋史乃,佐藤寛子,石井一之、越野広雪、橋爪大輔、Hans P. Luethi, Teodoro Laino, Juerg Hutter, 伊藤幸成
    • Organizer
      第54回天然有機化合物討論会
    • Place of Presentation
      東京農業大学、東京
    • Related Report
      2012 Research-status Report
  • [Presentation] グリコシル化反応の溶媒効果に関する理論的研究:オキサカルベニウムーカウンターイオン中鑑定の立体配座による立体選択性の制御2012

    • Author(s)
      佐藤寛子、ハルバー ハンセン、眞鍋史乃、ウィルフレッド ファン グンステレン、フィリップ ヒューネンベルガー
    • Organizer
      第6回分子化学討論会
    • Place of Presentation
      東京大学、東京
    • Related Report
      2012 Research-status Report
  • [Presentation] Pyranoside Conformational Effect on Reactivity and Selectivity in Glycosylation Reactions2012

    • Author(s)
      Shino Manabe, Kazuyuki Ishii, Hiroko Satoh, Daisuke Hashizume, Yukishige Ito
    • Organizer
      26th International Carbohydrate Symposium
    • Place of Presentation
      Madrid, Spain
    • Related Report
      2012 Research-status Report
  • [Presentation] Endo/Exo C-O Bond Cleavage Manners of Glycosides with 2,3-trans or 2,3-cis Cyclic Protecting Groups2012

    • Author(s)
      Hiroko Satoh, Shino Manabe, Yukishige Ito, Hans Peter Luethi, Teodoro Laino, Juerg, Hutter
    • Organizer
      26th International Carbohydrate Symposium
    • Place of Presentation
      Madrid, Spain
    • Related Report
      2012 Research-status Report
  • [Book] 糖鎖の新機能開発・応用ハンドブック ~創薬・医療から食品開発まで~立体選択的グリコシル化反応2015

    • Author(s)
      眞鍋史乃
    • Total Pages
      678
    • Publisher
      (株)エヌティーエス
    • Related Report
      2015 Annual Research Report
  • [Book] Glycoscience: Biology and Medicine2015

    • Author(s)
      Shino Manabe, Zhang Qingju, Ito Yukishige
    • Total Pages
      1556
    • Publisher
      Springer
    • Related Report
      2014 Research-status Report
  • [Book] Carbohydrate Chemistry: Proven Synthetic Methods2013

    • Author(s)
      Shino Manabe, Zhang Qingju, Ito Yukishige
    • Total Pages
      333
    • Publisher
      CRC Press
    • Related Report
      2013 Research-status Report
  • [Patent(Industrial Property Rights)] 糖鎖化合物および糖鎖化合物の製造方法2013

    • Inventor(s)
      眞鍋史乃、石井一之、佐藤寛子
    • Industrial Property Rights Holder
      眞鍋史乃、石井一之、佐藤寛子
    • Industrial Property Rights Type
      特許
    • Filing Date
      2013-08-30
    • Related Report
      2013 Research-status Report
    • Overseas
  • [Patent(Industrial Property Rights)] 糖鎖化合物および糖鎖化合物の製造方法2013

    • Inventor(s)
      眞鍋史乃、石井一之、佐藤寛子
    • Industrial Property Rights Holder
      独立行政法人理化学研究所、国立情報学研究所
    • Industrial Property Rights Type
      特許
    • Filing Date
      2013-03-01
    • Related Report
      2012 Research-status Report

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Published: 2013-05-31   Modified: 2022-02-16  

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