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1995 Fiscal Year Final Research Report Summary

Organic modeling of coenzymes of C_1-unit transfer

Research Project

Project/Area Number 05453038
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionWaseda University

Principal Investigator

TADA Masaru  Schl.Sci.Enginr, Waseda Univ. Professor, 理工学部, 教授 (90063651)

Project Period (FY) 1993 – 1995
Keywordsfolic acid / pteridine synthesis / radical substitution / cobaloxime / cobalt-sulfur interaction / methyl transfer / mixed disulfide
Research Abstract

This project concerns the modeling of coenzyme for C_1-unit transfer in biological system and consists of three sub-projects : (1) syntheses of folic acid models, (2) reaction of cobaloxime as a coenzyme-B_<12> model, and (3) the radical substitution on sulfur as a coenzyme-M model.
As to the first sub-subject, we developed two modes of pteridine syntheses from dicyanopyrizine. The key reaction of synthesis is the substitution of the cyano group with amines and the resulting amino-vcyanopyrazine was transformed into pteridine by methylisocyanate or guanidine. The pteridines thus obtained were further transformed into folic acid models by the radical substitution with anilinomethyl radical. As to the second sub-subject, we clarified the participation of cobalt (II) complex on the methyl transfer from methylcobaloxime to sulfur compounds. Spectroscopic study showed the strong interaction between cobalt (II) and sulfur.
As to the third sub-project, we simulated the transfer of methyl group from sulfur to nickel complex, which is a cozyme-M model, with concomitant formation of mixed disulfide.
These results cited above indicate the feasibility of the biological C_1-unit transferin an artificial systems and the developement of the reagents based on those concept can be possible.

  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] N. Kanomata,M. Igarashi,and M. Tada: "Nucleophilic Radical Substitution of Polychloroazines." Heterocycles. 35. 1127-1138 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Oikawa,N. Kanomata,and M. Tada: "Syntheses and Properties of 5-Substituted [n](2,4) Pyridinophanes,Model Compounds of NAN(P)." J. Org. Chem.58. 2046-2051 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Igarashi and M. Tada,: "Photochemical Arylaminomethylation of the Pyrazine Derivatives Having Electronegative Substituents." Heterocycles.38. 2277-2288 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Tada,N. Mutoh,and T. Shimizu: "Reaction of (3-Furylmethyl)-cobaloxime with Dienophiles. Variation by the Type of Dienophiles." J. Org. Chem.60. 550-553 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Igarashi and M. Tada: "Regioselective Synthesis of 6-Alkylated Lumazine Derivatives." J. Heterocycl. Chem.32. 807-810 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Tada and K. Kaneko: "The Effect of Cobalt(II) Complex on the Reactivity of Thioester in Radical Process." Chem. Lett.843-844 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Kanomata, M.Igarashi, and M.Tada: "Nucleophilic Radical Substitution of Polychloroazines." Heterocycles. 35. 1127-1138 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Oikawa, N.Kanomata, and M.Tada: "Syntheses and Properties of 5-Substituted [n] (2,4) Pyridinophanes, Model Compounds of NAN (P)." J.Org.Chem.58. 2046-2051 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Igarashi and M.Tada: "Photochemical Arylaminomethylation of the Pyrazine Derivatives Having Electronegative Substituents." Heterocycles. 38. 2277-2288 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tada, N.Mutoh, and T.Shimizu: "Reaction of (3-Furylmethyl)-cobaloxime with Dienophiles. Variation by the Type of Dienophiles." J.Org.Chem.60. 550-553 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Igarashi and M.Tada: "Regioselective Synthesis of 6-Alkylated Lumazine Derivatives." J.Heterocycl. Chem.32. 807-810 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tada and K.Kaneko: "The Effect of Cobalt (II) Complex on the Reactivity of Thioester in Radical Process." Chem.Lett.1995. 843-844

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tada, T.Yoshihara, and K.Sugano: "Radical Subatitution on a Thioester by a Methyl Radical Generated from Methyl (L) cobaloxime." J.Chem.Soc.Perkin.Tras.1. 1941-1944 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tada, K.Sugano, and T.Yoshihara: "Alkyl Radical Substitution on Disulfide in the Presence of Cobalt (II) Complex." Bull.Chem.Soc.Jpn.68. 2969-2973 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tada and R.Nagasaka: "Dual Nature of (Phenylseleno) cobaloxime in the Reaction with 2-Propynyl Derivatives." Bull.Chem.Soc.Jpn.68. 3221-3225 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Igarashi and M.Tada: "Regiospecific Synthesis of 6-Alkylated Lumazine Derivatives Using Silylenol Ether." Synthesis. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Igarashi, T.Kambe, and M.Tada: "Syntheses of Folic Acid Models, 6- (N-Acylarylamino) methyllumazines." J.Heterocycl.Chem.(in press).

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1997-03-04  

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