Fine Organic Synthesis with Nucleophilic Catalysts

• Project/Area Number: 18209001
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kyoto University
• Principal Investigator: KAWABATA Takeo Kyoto University, 化学研究所, 教授 (50214680)
• Co-Investigator(Kenkyū-buntansha): TSUBAKI Kazunori 京都大学, 化学研究所, 准教授 (50303897)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥39,390,000 (Direct Cost: ¥30,300,000、Indirect Cost: ¥9,090,000); Fiscal Year 2008: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2007: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2006: ¥31,070,000 (Direct Cost: ¥23,900,000、Indirect Cost: ¥7,170,000)
• Keywords: 位置選択性 / 求核触媒 / アシル化 / 糖 / ポリオール / 基質認識 / 無保護糖 / リン酸化 / 硫酸化 / グルクース / グルコース / 無保護

Research Abstract

ポリオールなどの多官能基性化合物の位置選択的な官能基化は現代有機化学が最も不得手としている分野で、信頼できる非酵素的手法は皆無に等しい。本研究では糖類の複数ある水酸基の位置選択的なアシル化を完全な選択性で起こす人工触媒の開発に成功した。本法の特徴は本来反応性の低い水酸基上で触媒主導による反応が進行すること、また第1級アルコールが共存しても、グルコースの2級水酸基のアシル化が優先する点である。

Research Products

• [Journal Article] Regioselective Acylation of Octyl β-D-Glucopyranoside by Chiral 4-Pyrrolidinopyridine Analogues (2008)
  • Author(s): T. Kawabata, W. Muramatsu, T. Nishio, T. Shibata, Y. Uruno, R. Stragies
  • Journal Title: Synthesis Pages: 747-753
  • Peer Reviewed
• [Journal Article] Regioselective Acylation of Octy β-D-Glucopyranoside by Chiral4-Pyrrolidinopyridine Analogues (2008)
  • Author(s): Kawabata, T., Muramatsu, W., Nishio, T., Uruno, Y., Stragies, R.
  • Journal Title: Synthesis Pages: 747-753
  • Peer Reviewed
• [Journal Article] An Organocatalytic Regioselecive Acylationof Carbohydrates: Toward the Development ofIntelligent Catalysts (2007)
  • Author(s): T. Kawabata
  • Journal Title: J. Syn. Org. Chem. Japan 65 Pages: 1081-1087
  • Peer Reviewed
• [Journal Article] A Catalytic One-Step Process for the Chemoand Regioselective Acylation of Carbohydrates (2007)
  • Author(s): T. Kawabata, W. Muramatsu, T. Nishio, T.Shibata, H. Schedel
  • Journal Title: J. Am. Chem. Soc 129 Pages: 12890-12895
  • Peer Reviewed
• [Journal Article] Regioselective Acylation of 6-O-protectedoctylβ-D-glucopyranosides by DMAP Catalysis (2007)
  • Author(s): W. Muramatsu, T. Kawabata
  • Journal Title: Tetrahedron Lett 48 Pages: 5031-5033
  • Peer Reviewed
• [Journal Article] Colorimetric Recognition of Length of α, ω-Diamines in Water (2007)
  • Author(s): K. Tsubaki, D. Tanima,T. Sasamori, N. Tokitoh, T. Kawabata
  • Journal Title: Tetrahedron Lett 48 Pages: 2135-2138
  • Peer Reviewed
• [Journal Article] Regioselective Acylation of Octy1 β-D-Glucopyranoside by Chiral 4-Pyrrolidinopyridine Analogues (2007)
  • Author(s): Kawabata, T.; Muramatsu, W.; Nishio, T.; Shibata, T.; Uruno, Y.; Stragies, R.
  • Journal Title: Synthesis Pages: 747-753
  • Peer Reviewed
• [Journal Article] An Organocatalytic Regioselective Acylation of Carbohydrates: Toward the Development of Intelligent Catalysts (2007)
  • Author(s): T. Kawabata
  • Journal Title: J. Syn. Org. Chem. Japan 65 Pages: 1081-1087
  • NAID: 10019787978
  • Peer Reviewed
• [Journal Article] A Catalytic One-Step Process for the Chemo-and Regioselective Acylation of Carbohydrates (2007)
  • Author(s): Kawabata T. Muramatsu, W. Nishio, T. Shibata, T. Schedel, H
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 12890-12895
  • Peer Reviewed
• [Journal Article] Regioselective acylation of 6-0-protected octyl beta-D-glucopyranosides by DMAP catalysis (2007)
  • Author(s): Muramatsu, W. Kawabata, T.
  • Journal Title: Tetrahedron Lett. 48 Pages: 5031-5033
  • Peer Reviewed
• [Journal Article] 魅力的な分子変換へのアプローチ (2007)
  • Author(s): 川端猛夫
  • Journal Title: ファルマシア 43 Pages: 242-244
• [Journal Article] Bidirectional and Colorimetric Recognition of Sodium and Potassium Ions (2006)
  • Author(s): K. Tsubaki, D.Tanima, Y. Kuroda, K. Fuji, T. Kawabata
  • Journal Title: Org. Lett 8 Pages: 5797-5800
  • Peer Reviewed
• [Journal Article] Long-Range Exciton-Coupled CircularDichroism: Application for Determination ofAbsolute Configuration of Oligonaphthalenes (2006)
  • Author(s): K.Tsubaki, K. Takaishi, H. Tanaka, M. Miura, T. Kawabata
  • Journal Title: Org. Lett 8 Pages: 2587-2590
  • Peer Reviewed
• [Journal Article] Visual Enantiomeric Recognition of AminoAcid Derivatives in Protic Solvents
  • Author(s): K. Tsubaki,D. Tanima, M. Nuruzzaman, T. Kusumoto, K.Fuji, T. Kawabata
  • Journal Title: J. Org. Chem Pages: 4609-4616
  • Peer Reviewed
• [Presentation] 鎖状ジオールの鎖長識別モノアシル化 (2009)
  • Author(s): 吉田圭佑、川端猛夫
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-27
• [Presentation] 求核触媒を用いるグルコース特異的アシル化 (2009)
  • Author(s): 三代憲司、川端猛夫
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-27
• [Presentation] C_2-対称求核触媒を用いる糖類の位置選択的官能基化 (2009)
  • Author(s): 上田善弘、川端猛夫
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-27
• [Presentation] C_2-対称求核触媒を用いるグルコース誘導体の位置選択的官能基化 (2008)
  • Author(s): 上田善弘、川端猛夫
  • Organizer: 第27回メディシナルケミストリーシンポジウム
  • Place of Presentation: 大阪
  • Year and Date: 2008-12-27
• [Presentation] 精密分子認識型アシル化触媒 (2008)
  • Author(s): 川端猛夫
  • Organizer: 第4回機能性分子シンポジウム
  • Place of Presentation: 筑波
  • Year and Date: 2008-12-20
• [Presentation] 精密分子認識型アシル化触媒 (2008)
  • Author(s): 川端 猛夫
  • Organizer: 第四回機能性分子シンポジウム
  • Place of Presentation: つくば
  • Year and Date: 2008-12-20
• [Presentation] SelectiveAcylation by Intelligent Nucleophilic Catalysis (2008)
  • Author(s): Takeo Kawabata
  • Organizer: UK/Japan Joint Symposium on Asymmetric Catalysis
  • Place of Presentation: Kyoto
  • Year and Date: 2008-12-09
• [Presentation] Selective Acylation by Intelligent Nucleophilic Catalysis (2008)
  • Author(s): Tokeo KAWABATA
  • Organizer: UK/Japan Joint Symposium on Asymmetric Catalysis 2008
  • Place of Presentation: kyoto
  • Year and Date: 2008-12-09
• [Presentation] 選択的脱保護可能なグルコース誘導体の効率的合成 (2008)
  • Author(s): 三代憲司、川端猛夫
  • Organizer: 第27回メディシナルケミストリーシンポジウム
  • Place of Presentation: 大阪
  • Year and Date: 2008-11-27
• [Presentation] インテリジェント触媒の開発を目指して : 動的分子認識に立脚した触媒設計 (2008)
  • Author(s): 川端猛夫
  • Organizer: 有機合成化学協会東海支部講演会
  • Place of Presentation: 岐阜
  • Year and Date: 2008-07-21
• [Presentation] 求核触媒を用いる遠隔位官能基識別アシル化 (2008)
  • Author(s): 菅慶三、川端猛夫
  • Organizer: 第6回次世代を担う有機化学シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2008-05-30
• [Presentation] σ-対称1, 9-ジオールの不斉非対称化に基づく触媒的不斉ラクトン化 (2008)
  • Author(s): 菅慶三、川端猛夫
  • Organizer: モレキュラー・キラリティー2008
  • Place of Presentation: 岡山
  • Year and Date: 2008-05-22
• [Presentation] 糖類への効率的な位置選択的保護基導入法の開発とその応用 (2008)
  • Author(s): 村松渉、川端猛夫
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-27
• [Presentation] Peptide[2]Catenaneの合成 (2008)
  • Author(s): 宇留野義治、椿一典、川端猛夫
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-27
• [Presentation] C_2-対称求核触媒を用いる糖-アミノ酸ハイブリッドの位置選択的合成 (2008)
  • Author(s): 上田善弘、川端猛夫
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-27
• [Presentation] Fine Molecular Transformation by Nucleophilic Catalysis (2007)
  • Author(s): Takeo Kawabata
  • Organizer: International Chemical Conference, Taipei, 2007(ICCT-2207)
  • Place of Presentation: Taiwan
  • Year and Date: 2007-12-15
• [Presentation] Fine Molecular Transformation by Nucleophilic Catalysis (2007)
  • Author(s): Takeo Kawabata
  • Organizer: International Chemical Conference, (Taipei), 2007(ICCT-2207)
  • Place of Presentation: National Tsing-Hua University, Hsinchu,(Taiwan)
  • Year and Date: 2007-12-05
• [Presentation] Ligation法を持ちいるペプチドカテナンの合成 (2007)
  • Author(s): 宇留野義治、椿一典、川端猛夫
  • Organizer: 第33回反応と合成の進歩シンポジウム
  • Place of Presentation: 長崎
  • Year and Date: 2007-11-05
• [Presentation] 糖類への効率的な一選択的保護基導入法の開発とその応用 (2007)
  • Author(s): 村松渉、川端猛夫
  • Organizer: 第33回反応と合成の進歩シンポジウム
  • Place of Presentation: 長崎
  • Year and Date: 2007-11-05
• [Presentation] C_2-対称キラル求核触媒を用いる不斉ラクトン化 (2007)
  • Author(s): 菅慶三, 川端猛夫
  • Organizer: 第57回日本薬学会近畿支部総会・大会
  • Place of Presentation: 大阪
  • Year and Date: 2007-11-05
• [Presentation] 糖類の直接的3位水酸基選択的アシル化 (2007)
  • Author(s): 村松渉、川端猛夫
  • Organizer: 第57回日本薬学会近畿支部総会・大会
  • Place of Presentation: 大阪
  • Year and Date: 2007-11-05
• [Presentation] 糖類への効率的な-選択的保護基導入法の開発とその応用 (2007)
  • Author(s): 村松 渉
  • Organizer: 第33回反応と合成の進歩シンポジウム
  • Place of Presentation: 長崎
  • Year and Date: 2007-11-05
• [Presentation] C2-対称キラル求核触媒を用いる不斉ラクトン化 (2007)
  • Author(s): 菅 慶三
  • Organizer: 第37回複素環化学討論会
  • Place of Presentation: 長野
  • Year and Date: 2007-10-18
• [Presentation] Kinetich Resolution of(±)-1, 1'-Binaphthyl-8, 8'-diamines by Chiral PPY Organocatalysts, Valluru Krishna Reddy (2007)
  • Author(s): Kazunori Tsubaki, Takeo Kawabata
  • Organizer: 第37回複素環化学討論会
  • Place of Presentation: 長野
  • Year and Date: 2007-10-09
• [Presentation] Kinetic Resolution of(±)-1, 1'-Binaphthyl-8, 8'-diamines by Chiral PPY Organocatalysts. V. K. Reddy (2007)
  • Author(s): Kazunori Tsubaki, Takeo Kawabata
  • Organizer: 12th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: ISNA-12, Awaji Island
  • Year and Date: 2007-10-09
• [Presentation] インテリジェント触媒の開発を目指して (2007)
  • Author(s): 川端猛夫
  • Organizer: 第34回有機反応懇談会
  • Place of Presentation: 大阪
  • Year and Date: 2007-07-27
• [Presentation] Kinetic Resolution of (±)-1,1'-Binaphthyl-8,8'-diamines by Chiral PPY Qrganocatalysts. (2007)
  • Author(s): Reddy Valluru Kurishna
  • Organizer: 12th International Symposium on Novel Aromatic Compounds (ISNA-12)
  • Place of Presentation: Awaji Island
  • Year and Date: 2007-07-23
• [Presentation] Kinetic Resolution of 1, 1'-BinaphthylAmines Using Chiral PPY Organocatalysts. Krishna Reddy Valluru (2007)
  • Author(s): 椿一典、川端猛夫
  • Organizer: 日本薬学会第127年会
  • Place of Presentation: 富山
  • Year and Date: 2007-03-30
• [Presentation] Chiral 8, 8'-diamino-2, 2'-dimethyl-1, 1'-binaphthyls : New Acylating Agents for Kinetic Resokution of Amines, Dinh Thi Thanh Hai (2007)
  • Author(s): 椿一典、川端猛夫
  • Organizer: 日本薬学会第127年会
  • Place of Presentation: 富山
  • Year and Date: 2007-03-30
• [Presentation] C_2-対称PPY型不斉求核触媒を用いる不斉ラクトン化 (2007)
  • Author(s): 柴田威、川端猛夫
  • Organizer: 日本薬学会第127年会
  • Place of Presentation: 富山
  • Year and Date: 2007-03-30
• [Presentation] Regioslective Acylation of Sugarsby C_2-Symmetric Chiral Nucleophilic Catalysts Wataru Muramatsu (2007)
  • Author(s): Takeo Kawabata
  • Organizer: GSC-AON 2007 Joint Meeting of The 1st Asian-Oceanian Conference on Green and Substainable Chemistry and The 7th Annual Green and Sustainable Chemistry Symposium
  • Year and Date: 2007-03-09
• [Presentation] Regioslective Acylation of Sugars by C2-Symmetric Chiral Nucleophilic Catalysts (2007)
  • Author(s): Wataru Muramatsu
  • Organizer: GSC-AON 2007 Joint Meeting of The 1st Asian-Oceanian Conference on Green and Substainable Chemistry and The 7th Annual Green and Sustainable Chemistry Symposium
  • Place of Presentation: Tokyo
  • Year and Date: 2007-03-06
• [Presentation] 不斉求核触媒を用いる糖類の位置選択的アシル化 (2006)
  • Author(s): 川端猛夫
  • Organizer: 第32回反応と合成の進歩シンポジウム
  • Place of Presentation: 広島
  • Year and Date: 2006-12-05
• [Presentation] Highly Regioselective Functionalization of Sugars by C2-Symmetric Chiral Nucleophilic Catalysts. Wataru, Muramatsu (2006)
  • Author(s): Takeo Kawabata
  • Organizer: IKCOC-10
  • Place of Presentation: Kyoto
  • Year and Date: 2006-11-04
• [Presentation] Regioselective Acylation of Sugars by Nucleophilic Catalysis (2006)
  • Author(s): Takeo Kawabata
  • Organizer: 45th Tutzing Symposion : Organocatalysis
  • Place of Presentation: Tutzing, Germany
  • Year and Date: 2006-10-11
• [Presentation] Direct Regioselective Acylation of Sugars BY C_2-Symmetric Chiral Nucleophilic Catalysts, Wataru Muramatsu (2006)
  • Author(s): Takeo Kawabata
  • Organizer: ICOB-5 & ISCNP-25 IUPAC International Conference on Biodiversity and Natural Products
  • Year and Date: 2006-07-24
• [Presentation] Colorimetric Recognition of Melecular Length in Water Based on Phenolphthalein Derivatives (2006)
  • Author(s): Kazunori Tsubaki, Daisuke Tanima, Takeo Kawabata
  • Organizer: ICOB-5 & ISCNP-25 IUPAC International Conference on Biodiversity and Natural Products
  • Year and Date: 2006-07-24
• [Presentation] ペプチドカテナンの合成研究DL-型キラリティーを利用する高次構造の構築 (2006)
  • Author(s): 宇留野義治、椿一典、川端猛夫
  • Organizer: 第23回有機合成セミナー
  • Place of Presentation: 北海道
  • Year and Date: 2006-07-13
• [Presentation] C_2-対称PPY型不斉求核触媒の合成および選択的反応 (2006)
  • Author(s): 柴田威, 川端猛夫
  • Organizer: 第23回有機合成セミナー
  • Place of Presentation: 北海道
  • Year and Date: 2006-07-13
• [Presentation] Structural and Functional Investigation of D,L-Oligomers (2006)
  • Author(s): Takeo Kawabata
  • Organizer: International Molecular Chirality Conference
  • Place of Presentation: Toyama
  • Year and Date: 2006-05-18
• [Presentation] Highly Regioselective Acylation of Sugars by Chiral Nucleophilic Catalysts (2006)
  • Author(s): Takeo Kawabata
  • Organizer: The 8th International Symposium on Organic Reactions
  • Place of Presentation: Kobe
  • Year and Date: 2006-04-24
• [Presentation] C_2-対称不斉求核触媒を用いる糖類の位置選択的アシル化 (2006)
  • Author(s): 村松渉, 川端猛夫
  • Organizer: 日本薬学会第126年会
  • Place of Presentation: 仙台
  • Year and Date: 2006-03-30
• [Presentation] ペプチドカテナンの合成研究:DL-型キラリティーを利用する高次構造の構築 (2006)
  • Author(s): 川端猛夫, 宇留野義治, 椿一典
  • Organizer: 日本薬学会第126年会
  • Place of Presentation: 仙台
  • Year and Date: 2006-03-30
• [Patent(Industrial Property Rights)] アルキルβ-D-(チオ)グルコピラノシド誘導体の位置選択的保護基導入方法 (2008)
  • Inventor(s): 川端猛夫
  • Industrial Property Rights Holder: 和光純薬工業株式会社、池添 太京都大学、尾池和夫
  • Industrial Property Number: 2008-109378
  • Filing Date: 2008-04-18