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Abstract

The first reported acyl and sulfonylisocyanates were developed and tested in reactions with chiral alcohols to afford diastereomeric carbamates. NMR analysis of these investigates the chemical shift discrimination that would allow these activated isocyanates to be used as diagnostic probes of enantiomeric purity.

Keywords

N.M.R Enantiomeric excess Isocyanates Camphor derivatives.

Article Details

References

  1. CONNOLLY, J. D. and HILL, R. A. 1991. Dictionary of Terpenoids,Vol 1. Wiley, New York, 151.
  2. DALE, J. A. and MOSHER, H. S. 1968. Nuclear Magnetic Resonance Nonequivalence of Diastereomeric Esters of α-Substituted Phenylacetic Acids for the Determination of Stereochemical Purity. J. Am. Chem. Soc. 90: 3732-3738.
  3. DALE, J. A., DULL, D. L. and MOSHER, H. S. 1969. α-Methoxy-α-trifluoromethylphenylacetic Acid, a Versatile Reagent for the Determination of Enantiomeric Composition of Alcohols and Amines. J. Org. Chem. 34: 2543-2549.
  4. DALE, J. A. and MOSHER, H. S. 1973. Nuclear Magnetic Resonance Enantiomer Reagents. Configurational Correlations via Nuclear Magnetic Resonance Shifts of Diastereomeric Mandelate, O-Methylmandelate and α-Methoxy-α-trifluoromethylphenylacetate (MTPA) Esters. J. Am. Chem. Soc. 95: 512-519.
  5. DONOVAN, A. R. and ROOS, G. H. P. 1996. Homochiral Activated Isocyanates as Chiral Derivatising Agents. Synth. Commun. 26: 4603-4615.
  6. GAWLEY, R. E. and AUBÉ, J. 1996. Tetrahedron Organic Chemistry Series Vol. 14 : Principles of Asymmetric Synthesis. Pergamon, Oxford.
  7. JÄHCHEN, G. and WESTPHAL, G. 1969. Zur Darstelling von p-Toluolsulfinylisocyanat. Z. Chem. 9: 305.
  8. KOCIENSKI, P. J. and KIRKUP, M. 1975. Reaction of Nitrimines with Cyanide Ions. J. Org. Chem. 40: 1681-1682.
  9. KURZER, F. 1963. p-Toluenesulfinyl Chloride. Organic Syntheses, Collective Volume. 1V. Ed. N. Rabjohn. Wiley, New York, 937-939.
  10. LYLE, G. G. and LYLE, R. E. 1983. Polarimetry. In Asymmetric Synthesis Vol. 1, Ed J. D. Morrison. Academic Press, New York.
  11. MONEY, T. 1985. CAMPHOR: A Chiral Starting Material in Natural Product Synthesis. Nat. Prod. Rep. 2: 253
  12. PARKER, D. and TAYLOR, R. J. 1994. Analytical methods: determination of enantiomeric purity. In Asymmetric Synthesis eds R. A. Aitken and S. N. Kilenyi. Blackie, Glasgow.
  13. PARKER, D. 1991. NMR Determination of Enantiomeric Purity. Chem. Rev. 91: 1441-1457.
  14. PASSERINI, M. 1925. Reazione del cianuro di potassio con I pernitroso derivati. Gazz. Chim. Ital. 55: 559-567.
  15. ROOS, G. H. P. and WATSON, M. C. 1991. Trichloroacetyl isocyanate: rapid in situ determination of diastereomeric ratios of alcohols by 1H NMR spectroscopy. S. Afr. J. Chem. 44: 95-96.
  16. ROOS, G. H. P., MANICKUM, T. and MALISSAR, D. G. 1992. A Facile Diagnostic 1H NMR Method for syn and anti Hydroxy Systems. J. Chin. Chem. Soc. 39: 105-106.
  17. ROOS, G. H. P., MANICKUM, T., FIELD, J. S. and RAMESAR, N. 1994. X-Ray crystallographic confirmation of the stereo-substructure determination by NMR spectroscopy of two diastereoselective Baylis-Hillman reaction products. S. Afr. J. Chem. 47: 33-35.
  18. SCHNEIDER, H., WEIGAND, E. F. and BECKER, N. 1988. Linear Electric Field Effects on 13C NMR Shifts in Saturated Aliphatic Frameworks: Scope and Limitations. J. Org. Chem. 53: 3361-3364.
  19. WHITMORE, F. C. and HAMILTON, F. H. 1941.Organic Syntheses, Collective Volume1.(2nd Edition).Ed.A. H. Blatt.Wiley,New York : 492-494.
  20. YAMAGUCHI, S. 1983. Nuclear Magnetic Resonance Analysis Using Chiral Derivatives. In Asymmetric Synthesis Vol. 1, Ed J. D. Morrison. Academic Press, New York.