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Stereoselective Glycosylation via Decarboxylation of Mixed Carbonate

Research Project

Project/Area Number 08672446
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTeikyo University

Principal Investigator

OHTAKE Hiro (1997)  Teikyo University Faculty of Pharmaceutical Sciences Research Associate, 薬学部, 助手 (50256054)

飯森 隆昌 (1996)  帝京大学, 薬学部, 助教授 (90246025)

Co-Investigator(Kenkyū-buntansha) AZUMAYA Isao  Teikyo University Faculty of Pharmaceutical Sciences Research Associate, 薬学部, 助手 (50276755)
TAKAHASHI Hideyo  Teikyo University Faculty of Pharmaceutical Sciences Research Associate, 薬学部, 助手 (10266348)
大竹 廣雄  帝京大学, 薬学部, 助手 (50256054)
Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1997: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1996: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsGlycosylation / Decarboxylation / Carbonates / Benzyl protected sugars / Acyl protected sugars / Hafnocene dichloride / Silyl triflate / Tin (IV) chloride / ベンジル保護糖
Research Abstract

While study of the interglycosidic bond formation has been rapidly expanded, high-yielding and stereoselective glycosylation methods have been developed thus far. These glycosidic bond formations are generally based on the activation of glycosyl donors with leaving groups by appropriate promoters, but a different type of glycosylation is an engaging alternative, which can furnish flexible strategies for oligosaccharide synthesis. Along this line, we developed a decarboxylative glycosylation method which involves 1) linking two sugar moieties using carbonate as a connector and 2) removing internal carbon dioxide by the aid of Lewis acid to form glycosidic bond.
First, we searched suitable activating (leaving) groups for the synthesis of glycosyl carbonates. Using 4-nitrophenyl carbonates as active carbonates, the mixed carbonates of benzyl protected sugars were prepared in good yields. The imidazolides could be also used when a tedious chromatographic separation was needed to remove a by-product (bis (4-nitrophenyl) carbonate). In the case of acyl sugars, succinimidyl carbonates generally gave the best yield and beta-selectivity at the anomeric position, which effected beta-selectivity in the next glycosylation.
In surveying promoters, various Lewis acids were found to cause decarboxylative glycosylation. An equimoler amount of TMSOTf promoted the decarboxylation of benzyl protected glycosyl carbonates in toluene to form glycosides beta-preferentially (-1 : 4). The reaction proceeded by a catalytic amount of TMSOTf, though the lower selectivity was observed because of the longer reaction time. The combination of SnCl_4-AgClO_4 or Cp_2HfCl_2-2AgClO_4 catalytically promoted the decarboxylation in ether to give glycosides alpha-selectively (8 : 1-19 : 1). Acyl protected mixed carbonates obtained as beta-anomer were promoted by an equimoler amount of TMSOTf in dichloromethane to give the corresponding pure beta-glycoside in high yield.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] Takamasa Iimori: "A Mild and Rapid Glycosylation Reaction between Pyrimidine Bases and 2-Deoxyribofuranosyl N,N,N′,N′-Tetramethylphosphoroamidates" Heterocycles. 42. 485-488 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "Palladium Chloride Mediated Rearrangement of 6-Deoxyhex-5-enopyranosides into Cyclohexanones" Tetrahedron Letters. 37. 649-652 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Toru Sasaki: "Regioselective Acetylation of 7-Deacetylforskolin with ^<11>C-Acetyl Chloride" Journal of Labelled Compounds and Radiopharmaceuticals. XXXVIII. 337-347 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Novel Intramolecular Decarboxylative Glycosylation via Mixed Carbonate" Tetrahedron Letters. 37. 2267-2270 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Practical Preparation of Optically Active endo-Bicyclo [3.3.0] octen-2-ols" Chemical & Pharmaceutical Bulltein. 45. 207-208 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Hiro Ohtake: "A Facile and Improved Preparation of Glycosylidene Acetals of Monosaccharides" Tetrahedron Letters. 38. 3413-3414 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Highly Stereoselective β- (1→4) -Glycosidic Bond Formation by Reductive Cleavage of Cyclic Orthoesters" Tetrahedron Letters. 38. 3415-3418 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "An α-Selective Glycosylation via Decarboxylation of Mixed Carbomate Catalyzed by the Combination of Lewis Acid and Silver Perchlorate" Heterocycles. 46. 221-224 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Hiro Ohtake: "Synthesis and Structure of Glycosylidene Acetals of Galactoside" Heterocycles. 47 (in press). (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Mild and Rapid Glycosylation Reaction Between Pyrimidine Bases and 2-Deoxyribofuranosyl N,N,N', N'-Tetramethylphosphroamidates" Heterocycles. 42 (2). 485-488 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "Palladium Chloride Mediated Rearrangement of 6-Deoxyhex-5-enopyranosides into Cyclohexanones" Tetrahedron Lett.37 (5). 649-652 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Toru Sasaki: "Regioselective Acetylation of 7-Deacetylforskolin with ^<11>C-Acetyl Chloride" J.Labelled Compds.and Radiopharmaceuticals. XXXVIII (4). 337-347 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Novel Intramolecular Decarboxylative Glycosylation via Mixed Carbonate" Tetrahedron Lett.37 (13). 2267-2270 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Practical Preparation of Optically Active endo-Bicyclo [3.3.0] octan-2-ols" Chem.Pharm.Bull.45 (1). 207-208 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Hiro Ohtake: "A Facile and Improved Preparation of Glycosylidene Acetals of Monosaccharides" Tetrahedron Lett.38 (19). 3413-3414 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Highly Stereoselective beta-(1*4)-Glycosidic Bond Formation by Reductive Cleavage of Cyclic Orthoesters" Tetrahedron Lett.38 (19). 3415-3418 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "An alpha-Selective Glycosylation via Decarboxylation of Mixed Carbonate Catalyzed by the Combination of Lewis Acid and Silver Perchlorate" Heterocycles. 46. 221-224 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Hiro Ohtake: "Synthesis and Structure of Glycosylidene Acetals of Galactoside" Heterocycles. 47 (in press). (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takamasa Iimori: "A Mild and Rapid Glycosylation Reaction between Pyrimidine Bases and 2-Deoxyribofuranosyl N,N,N',N'-Tetramethylphosphoroamidates" Heterocycles. 42. 485-488 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takamasa Iimori: "Palladium Chloride Mediated Rearrangement of 6-Deoxyhex-5-enopyranosides into Cyclohexanones" Tetrahedron Letters. 37. 649-652 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Toru Sasaki: "Regioselective Acetylation of 7-Deacetylforskolin with ^<11>C-Acetyl Chloride" Journal of Labelled Compounds and Radiopharmaceuticals. XXXVIII. 337-347 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takamasa Iimori: "A Novel Intramolecular Decarboxylative Glycosylation via Mixed Carbonate" Tetrahedron Letters. 37. 2267-2270 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takamasa Iimori: "A Practical Preparation of Optically Active endo-Bicyclo[3.3.0]octen-2-ols" Chemical & Pharmaceutical Bulltein. 45. 207-208 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Hiro Ohtake: "A Facile and Improved Preparation of Glycosylidene Acetals of Monosaccharides" Tetrahedron Letters. 38. 3413-3414 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takamasa Iimori: "A Highly Stereoselective β-(1→4)-Glycosidic Bond Formation by Reductive Cleavage of Cyclic Orthoesters" Tetrahedron Letters. 38. 3415-3418 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takamasa Iimori: "An α-Selective Glycosylation via Decarboxylation of Mixed Carbonate Catalyzed by the Combination of Lewis Acid and Silver Perchlorate" Heterocycles. 46. 221-224 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Hiro Ohtake: "Synthesis and Structure of Glycosylidene Acetals of Galactoside" Heterocycles. 47(in press). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Toru Sasaki: "1-Acetyl-7-deacetylforskolin : A Potential Non-Specific Inactive Analog of Forskolin for Estimation of its Specific High-Affinity Binding and Adenylyl Cyclase Stimulation in vitro." Life Science. 57. 1367-1373 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takamasa Iimori: "A Mild and Rapid Glycosylation Reaction between Pyrimidine Bases and 2-Deoxyribofuranosyl N,N,N',N'-Tetramethylphosphoroamidates" Heterocycles. 42. 485-488 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takamasa Iimori: "Palladium Chloride Mediated Rearrangement of 6-Deoxyhex-5-enopyranosides into Cyclohexanones" Tetrahedron Letters. 37. 649-652 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takamasa Iimori: "A Novel Intramolecular Decarboxylative Glycosylation via Mixed Carbonate" Tetrahedron Letters. 37. 2267-2270 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takamasa Iimori: "A Practical Preparation of Optically Active endo-Bicyclo [3,3,0] octen-2-ols" Chemical & Pharmaceutical Bulltein. 37. 207-208 (1997)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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