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特異な構造をもつRNAの化学合成と反応

Research Project

Project/Area Number 04226105
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionNagoya University

Principal Investigator

早川 芳宏  名古屋大学, 人間情報学研究科, 教授 (50022702)

Co-Investigator(Kenkyū-buntansha) 沢井 宏明  群馬大学, 工学部, 教授 (70012648)
清水 剛夫  京都大学, 工学部, 教授 (10025893)
石戸 良治  東京薬科大学, 薬学部, 教授 (60016037)
畑 辻明  東京工業大学, 総合理工学研究科, 教授 (00016049)
Project Period (FY) 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥45,600,000 (Direct Cost: ¥45,600,000)
Fiscal Year 1993: ¥22,600,000 (Direct Cost: ¥22,600,000)
Fiscal Year 1992: ¥23,000,000 (Direct Cost: ¥23,000,000)
KeywordsCMP-シアル酸 / キャップ構造 / 2'-O-D-リボフラノシルアデノシン / オリゴヌクレオチドP(V)ポリフィリン誘導体 / 人工光制限酵素 / 5'-ポリリン酸ヌクレオチド / 人工制限酵素 / リン酸トリエステル修飾DNA / オリゴヌクレオチド / ヌクレオチドリンポルフィリン誘導体 / オリゴチオアデニル酸 / アンチセンス核酸 / 2-5A
Research Abstract

細胞表面の糖脂質や糖タンパク質の糖鎖末端を、細胞認識に深く関わるシアル酸で酵素的に修飾するための鍵物質であるシチジン-5'-リン酸-シアル酸(CMP-シアル酸)の化学合成に世界で初めて成功するとともに種々のCMP-シアル酸人工誘導体の合成が可能な一般合成法を開発した(早川、畑)。二官能性ホスホリル化剤、O-[8-(5-クロロキノリル)]S-フェニルホスホロチオエートを開発し、これを用いて、真核生物メッセンジャーRNAのキャップ構造部位のオリゴヌクレオチド、m^7G^5pppGおよびm^7G^5pppAを、ヌクレオシドに全く保護基を用いずに大量合成する方法を開発した(畑)。Yeast initiator tRNA^<Met>の構成成分として見い出されている2'-O-(α-およびβ-D-リボフラノシル)アデノシン、ならびにNMRによる核酸構造研究に有用な(2'R)-ならびに(2'S)-[2'-H^2]-2'-デオキシリボヌクレオシドおよび塩基部環外アミノ基^<15>N標識ヌクレオシドの効率的合成法を確立した(石戸)。オリゴヌクレオチド末端をリン(V)ポルフィリンで修飾した新規な光活性オリゴヌクレオチド誘導体を合成し、ピレン-オリゴヌクレオチド誘導体間の直接電子移動を介したオリゴヌクレオチドのシーケンス検出法を創案、実行した。またリン(V)ポルフィリンをオリゴヌクレオチドの主鎖に嵌めた新規な光活性オリゴヌクレオチドを合成し、ポルフィリン部が光誘起直接電子移動によるDNAの切断を行なうことを明かにし、人工制限酵素合成の可能性を示した(清水)。中性条件下、ホリホトリイミダゾリドあるいはホスホトリベンズイミダゾリドをリン酸供与体に、Mg(II)あるいはMn(II)イオンを触媒に用い、ATP、ADP、あるいは2-5Aなどのモノおよびオリゴヌクレオチドの5'-ポリリン酸化物を、対応する5'-モノヌクレオチド類から効率良く調製する方法を開発した(沢井)。

Report

(2 results)
  • 1993 Annual Research Report
  • 1992 Annual Research Report
  • Research Products

    (41 results)

All Other

All Publications (41 results)

  • [Publications] M.Uchiyama: "O-Selective Phosphorylation of Nucleosides without N-protection" J.Org.Chem.58. 373-379 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] S.Makino: "Chemical Synthesis of Cytidine-5'-monophosphono-N-acetylneuraminic Acid(CMP-Neu5Ac)" Tetrahedron Lett.34. 2775-2778 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Y.Hayakawa: "O-Allyl Protection of Guanosine and Thymidine Residues in Oligodeoxyribonucleotide Synthesis" J.Org.Chem.58. 5551-5555 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Hirose: "Synthesis of Phenylphosphonodiester-Modified Oligodeoxyribonucleotides via the Allyl Protection" Nucleic Acids Symp.Ser.29. 7-8 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Y.Hayakawa: "Allyl Protection in the Synthesis of Oligodeoxyribonucleotide Phosphorothioates" Nucleosides Nucleotides. 13 発表予定. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Sekine: "P-S Bond Formation Between Deoxyribonucleoside Phosphodiesters and Thiols by Means of BTCP" Natural Product Lett.1. 293-298 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Wada: "Nucleoside 3'-N,N-Dialkylphosphonamidates as Novel Nucleotide Units for Solution-Phase Oligonucleotide Synthesis" Tetrahedron. 49. 2043-2054 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Y.Ueno: "Studies on the Synthesis of Nucleotidyl-peptide Having 5'-Nucleotidyl-(P-O)-serine Phosphodiester Bond" Nucleic Acids Res.21. 4451-4457 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Fukuoka: "Convenient and Large Scale Synthesis of the Cap Structure,m^7G^<5'>pppG" Nucleic Acids Symp.Ser.29. 35-36 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Fukuoka: "One-Pot Reaction for the Synthesis of m^7G^<5'>pppG and m^7G^<5'>pppA by Using an Activatable Bifunctional Phosphorylating Reagent" Tetrahedron Lett.36 発表予定. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Fukuoka: "Large Scale Synthesis of the Cap part in Messenger RNA Using a New Type of Bifunctional Phosphorylating reagent" Nucleosides Nucleotides. 13 発表予定. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Segawa: "One-Dimensional Donor Acceptor Phosphorus Porphyrins Linked with Molecular Wire" Synth.Metal. 55-57. 966-971 (199)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Saito: "Photochemical Cleavage of DNA by Phosphorus(V)porphyrin Derivatives" Nucleic Acids Symp.Ser.29. 127-128 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Saito: "Photochemical Cleavage of DNA with Phosphorus(V)porphyrin derivatives" Nucleosides Nucleotides. 13 発表予定. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Sawai: "Mg(II)Ion-Mediated Conversion of Mono- and Oligonucleotides to 5'-Polyphosphates in Aqueous Solution" Tetrahedron Lett.34. 4801-4804 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Shimazu: "UO_2^<2+> Catalyzed Oligothioadenylate Synthesis with High Regio- and Stereoselectivity" Angew.Chem.Int.Ed.32. 870-872 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Shinozuka: "Bifunctional Labeling of DNA with Tris(2-aminoethyl)amine-derived Novel Fluorescent Agent" Bioorg.Med.Chem.Lett.13. 2883-2886 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] J.Seki: "Double and Triple Helix Formation of 2'-5' and 3'-5' Oligonucleotides" Nucleic Acids Symp.Ser.29. 71-72 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Shinozuka: "Non-radioisotope Labeling of DNA with Multifunctional Labeling Agent" Nucleic Acids Symp.Ser.29. 73-74 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Hirai: "Synthesis of New Copper-Complex of Macrocyclic Compound Consisting of 1,10-Phenanthroline,and Its DNA Binding and Cleaving Activity" Bull.Chem.Soc.Jpn.67 発表予定. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] R.Noyori: "Practical Synthesis of 2'-5'-Linked Oligoadenylates(2-5A Oligoners)." Austr.J.Chem.45. 205-225 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Hayakawa: "Partial Methyl Phosphotriester-modification of Oligodenxyribo-nucleotides." Nucleic Acids Symp.Ser.27. 103-104 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Uchiyama: "O-Selective Phosphorylation of Nucleosides without N-Protection." J.Org.Chem. 58. 373-379 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] R.Iwase: "Molecular Design of a Eukaryotic Messenger RNA and Its Chemical Synthesis." Nucleic Acids Res.20. 1643-1648 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Ueno: "Synthesis of 2'(3')-O-(L-Phenylalanyl)and 2'(3')-O-(D-Phenyl-alanyl)Dytidylyl(3'-5)adenosine." Chem.Lett.595-598 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Ohuchi: "Transformation of Dinucleoside S-Aryl Phosphorothioates into the Corresponding O-Alkyl Phosphates by Use of Tributyltin Alkoxides." Chem.Lett.1501-1504 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Ohuchi: "Facile Chlorination of Suger Moiety of Nucleosides by Use of Tris(2,4,6-tribromophemoxy)dichlophoshorane." Chem.Lett.1505-1506 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Ohuchi: "O-Alkylation of Dialkyl Phosphates and O-Alkyl Phosphonates via the Stannyl Intermediates." Nucleosides & Nucleotides. 11. 749-757 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Makino: "Chemical Synthesis of Cytidine-5'-monophosphono-N-acetyl-neuraminic Acid(CMP-Neu5Ac)." Tertahedron Lett.34. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Wada: "Nucleoside 3'-N,N-Dialkyphosphonamedates as Noves Nucleotide Units for the Solution-Shase Oligonucleotide Synthesis." Tetrahedron. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Shimidzu: "Syntheses of Oligonucleotide Derivatives with P(V)-Porphyrin and Their Properties." Nucleic Acids Symp.Ser.27. 97-98 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Kitamura: "Chiral Phosphoromorphidate Derivatives of Oligothymidylate and Their Hydridization Abilities." Nucleosides & Nucleotides. 11. 473-482 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Segawa: "Synthesis of Axial Dialkoxy Phosphorus(V)porphyrin Derivatives.Novel Hypervalent Phosphorus Compounds." J.Chem.Soc.,Perkin Trans.1. 939-940 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Segawa: "Phosphoinduced Axial Bond Exchange Reaction of Dichloro-Phosphorus(V)tetraphenylprophyrin Chloride:Photochemical Activation of Central Three-centre Four-electron Bond through the" J.Chem.Soc.,Chem.Commun.1066-1067 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Kunimoto: "Selective Synthesis of Unsymmertrical Dialkoxyphosphorus(V)-tetraphenylporphine Derivatives by Stepwise Substitution of Axial Position." Tetrahedron Lett.33. 6327-6330 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Kamaike: "Further Improvement in the Procedure for Oligonucleotide Synthesis in Terms of a Cellulose Acetate Derivative as a Polymer-support." Nucleosides & Nucleotides. 11. 637-668 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Sawai: "Synthesis of Cyclic and Acyclic Oligocytidylates by Uranyl Ion Catalyst in Aqueous Solution." J.Chem.Soc.,Perkin Trans.1. 505-508 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Sawai: "Divalent Metal Ion-Catalyzed Prophoshate Bond Formation in Aqueous Solution.Synthesis of Nucleotides Containing Polyphosphate." Nucleosides & Nucleotides. 11. 773-785 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Hirai: "Synthesis and DNA Cleaving Activity of Copper Complex of Macrocyclic Compound Containing 1,10-Phenanthroline." Chem.Lett.2023-2026 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Shimazu: "Facile an Stereoselctive Synthesis of 2'-5' Oligothioadenylates by UO_2^<2+>Ion Catalyst." Nucleic Acids Symp.ser.27. 105-106 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Shinozuka: "Temperature Dependent Duplex Formation of 3'-Phosphate Bearing α-2'-Deoxyoctathymidylate Phosphorothioate and Polyriboadenylic Acid Complex." Chem.Lett.2209-2212 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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