• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

PREPARATION OF AMINO ACIDS LABELED AT SPECIFIED POSITION FOR LABORATORY USE

Research Project

Project/Area Number 59850142
Research Category

Grant-in-Aid for Developmental Scientific Research

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

YOSHIKAWA Sadao  東京大学, 工, 教授 (70010759)

Project Period (FY) 1984 – 1985
Project Status Completed (Fiscal Year 1985)
Budget Amount *help
¥7,800,000 (Direct Cost: ¥7,800,000)
Fiscal Year 1985: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1984: ¥5,200,000 (Direct Cost: ¥5,200,000)
KeywordsAsymmetric Synthesis / Aminoacidato Complex / Amino Alkylmalonato Complex / 部分的重水素化による【^(13)C】シグナルの分裂
Research Abstract

On decarboxylation, <(+)_(577)> -(Co(AMM)((4R,6R)-4,6-dimethy1-3,7-diaza-1,9-diaminononane)) <ClO_4> . <H_2O> (1) resulted in 34% R-alaninato and 66% S-alaninato, while <(-)_(546)> -(Co(AMM)((6R,8R)-6,8-dimethy1-2,5,9,12-tetraazatridecane))Br. <3H_2O> (2) resulted in 83% R-alaninato and 17% S-alaninato, where AMM represents an <alpha> -amino- <alpha> -methyl-malonato ion. Two X-ray crystal structure determinations of (1) and (2) have been performed. The results suggest that the important factor which governs the stereoselectivity on decarboxylation, is not the coordination geometry of AMM in the starting complex, but the asymmetric environment around the AMM chelate. The decarboxylation of the AMM complexes using DCl yielded <alpha> -deuterated alaninato complexes.
The reaction of <alpha> -aminomalonate (AM) with trans dichloro(3,7-diaza-1,9-nonanediamine)cobalt(III) perchlorate yielded unexpectedly N-(2-aminoethyl)-N-(4-aza6-aminohexyl)( <alpha> , <alpha> -diaminomalonate)cobalt(III) perchlorate. The X-ray crystal structure revealed that the complex has an unusually stable geminal diamine linkage containing an uncoordinated primary amino group, as a result of the new bond formation between the <alpha> -carbon of the <alpha> -aminomalonate unit and one of the secondary nitrogens of the tetraamine ligand.
The first obeservation of isotopic multiplets in the <^(13)CNMR> spectra of the cobalt(III) complexes with partially deutrated coordinated <NH_2> or NH groups have been achieved. It has been found that the magnitude of the three bond isotope effect is governed both by the type of the observed carbon atoms and by the dihedral angle C-C-N-H.

Report

(1 results)
  • 1985 Final Research Report Summary
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] J.Am.Chem.Soc.107. (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1985 Final Research Report Summary
  • [Publications] J.Am.Chem.Soc.108. (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1985 Final Research Report Summary
  • [Publications] Inorg.Chem.25. (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1985 Final Research Report Summary
  • [Publications] J. Am. Chem. Soc. 107. (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1985 Final Research Report Summary
  • [Publications] J. Am. Chem. Soc.108. (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1985 Final Research Report Summary
  • [Publications] Inorg. Chem.25. (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1985 Final Research Report Summary

URL: 

Published: 1987-03-31   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi