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Amino Acids

, Volume 6, Issue 1, pp 97–105 | Cite as

Chirospecific synthesis of D and Lp-chlorohomophenylalanine N-t-BOC DCHA salts

  • J. W. Cessac
  • P. N. Rao
  • H. K. Kim
Article

Summary

The chirospecific conversions of D-glucosamine hydrochloride and D-mannosamine hydrochloride to the configurationally stable L and D isomers of N-t-butyloxycarbonylserinal were carried out byt-butylcarbonylation followed by sodium borohydride reduction and sodium meta-periodate oxidation. Reaction of the L and D aldehydes with the Wittig reagent prepared from 4-chlorobenzyltriphenylphosphonium chloride and butyl lithium followed by catalytic hydrogenation, Jones oxidation and salt formation with dicyclohexylamine gave the DCHA salts of the D and L isomers ofp-chlorohomophenylalanine N-t-Boc in high enatiomeric excess. The optical purity of the title compounds was established by hydrolysis to the respective free amino acids, followed by chiral derivatization and HPLC analysis.

Keywords

Amino acids Chirospecific D-Glucosamine hydrochloride D-Mannosamine hydrochloride L-N-t-Butyloxycarbonylserinal D-N-t-Butyloxycarbonylserinal D-p-Chlorohomophenylalanine N-t-Boc DCHA salt L-p-Chlorohomophenylalanine N-t-Boc DCHA salt 

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References

  1. Carlsen PHJ, Katsuki T, Martin US, Sharpless KB (1981) A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds. J Org Chem 46: 3936–3938Google Scholar
  2. Folkers K, Bowers CY, Kubiak T, Stepinski J (1983) Antagonist of the luteinizing hormone releasing hormone with pyridyl-alanines which completely inhibit ovulation at nanogram dosage. Biochem Biophys Res Commun 111: 1089–1095Google Scholar
  3. Giannis A, Henk T (1990) Chirospecific synthesis of amino acids, amino aldehydes and amino alcohols from D-glucosamine hydrochloride. A multigram synthesis of N-BOC-L-Serinal. Tetrahedron Lett 31: 1253–1255Google Scholar
  4. Karten MJ, Rivier JE (1986) Gonadotropin-releasing hormone analog design. Structurefunction studies toward the development of agonists and antagonists: Rational and perspective. Endocr Rev 7: 44–66Google Scholar
  5. Kinoshita T, Kasahara Y, Noriyuki N (1981) Reversed-phase high performance liquid chromatographic resolution of non-esterified enantiomeric amino acids by derivatization with 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate and 2,3,4-tri-O-acetyl-α-D-arabinopyranosyl isothiocyanate. J Chromatogr 210: 77–81Google Scholar
  6. Ljungqvist A, Feng DM, Bowers C, Hook WA, Folkers K (1990) Antagonists of LHRH superior to antide; effective sequence/activity relationships. Tetrahedron 46: 3297–3304Google Scholar
  7. Loev B, Goodman MM (1970) “Dry-column” chromatography. Prog Separ Purif 3: 73–95Google Scholar
  8. Nimura N, Orura H, Kinoshita T (1980) Reversed-phase liquid chromatographic resolution of amino acid enantiomers by derivatization with 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate. J Chromatogr 202: 375–379Google Scholar
  9. Pozdnev VF (1980) Introduction of tert-alkoxycarbonylamino-substituted groups into amino sugars using di-tert-alkylpyrocarbonates. Khim Prir Soedin 3: 408–409Google Scholar
  10. Weller HN, Gordon EM (1982) Absolute configuration of 2-amino-4-phenylbutyric acid (homophenylalanine). J Org Chem 47: 4160–4161Google Scholar
  11. Williams RM (1989) Synthesis of optically activeα-amino acids, 1st edn. Pergamon, New York, p 134Google Scholar

Copyright information

© Springer-Verlag 1994

Authors and Affiliations

  • J. W. Cessac
    • 1
  • P. N. Rao
    • 1
  • H. K. Kim
    • 2
  1. 1.Department of Organic ChemistrySouthwest Foundation for Biomedical ResearchSan AntonioUSA
  2. 2.Contraceptive Development Branch, National Institute of Child Health and Human DevelopmentNational Institutes of HealthBethesdaUSA

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