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DOI: 10.1039/A604677K (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 787-794

Addition reactions of alkenes with electronegatively substituted alcohols in the presence of xenon difluoride

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Melvin L. Druelinger, Dale F. Shellhamer, Robert D. Chapman, Scott A. Shackelford, Maurice E. Riner, Steven L. Carter, Ryan P. Callahan and Cameron R. Youngstrom

Abstract

The electrophilic reactivity of proposed alkoxyxenon fluoride (ROXeF) intermediates based on electronegatively substituted (polyfluorinated and polynitroaliphatic) alcohols has been characterized with model alkenes norbornene, 2-methylpent-1-ene and hex-1-ene. The alkoxyxenon fluorides can react as positive oxygen electrophiles—initially incorporating alkoxy substituents—or as apparent fluorine electrophiles—resulting in initial fluorine incorporation—depending on conditions. Efficient simple addition of poorly nucleophilic alcohols to norbornene was observed in certain systems. Selectivity between the various reaction paths (simple fluorination, alkoxyfluorination or alcohol addition) was observed to be a sensitive function of various reaction conditions, especially solvent, temperature and catalyst.

References

  1. D. F. Shellhamer, C. M. Curtis, R. H. Dunham, D. R. Hollingsworth, M. L. Ragains, R. E. Richardson, V. L. Heasley, S. A. Shackelford and G. E. Heasley, J. Org. Chem., 1985, 50, 2751 CrossRef CAS.
  2. D. F. Shellhamer, S. L. Carter, R. H. Dunham, S. N. Graham, M. P. Spitsbergen, V. L. Heasley, R. D. Chapman and M. L. Druelinger, J. Chem. Soc., Perkin Trans. 2, 1989, 159 RSC.
  3. (a) M. J. Kamlet, USP 3 541 160/ 1970; (b) F. E. Martin, USP 3 629 338/ 1971; (c) H. M. Peters and R. L. Simon, Jr., USP 3 922 311/ 1975.
  4. V. V. Avdonin, E. P. Kirpichev, Yu. I. Rubtsov, M. A. Fadeev, G. V. Oreshko and L. T. Eremenko, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1991, 2189 Search PubMed.
  5. Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications, eds. R. Filler, Y. Kobayashi and L. M. Yagupolskii, Elsevier, Amsterdam, 1993 Search PubMed.
  6. B. K. Park and N. R. Kitteringham, Drug Metab. Rev., 1994, 26, 605 CAS.
  7. M. Zupan, A. Gregorčič and A. Pollak, J. Org. Chem., 1977, 42, 1562 CrossRef CAS.
  8. S. A. Shackelford, J. Org. Chem., 1979, 44, 3485 CrossRef CAS.
  9. L. T. Eremenko and F. Ya. Natsibullin, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1968, 875 Search PubMed.
  10. M. J. Kamlet and H. G. Adolph, J. Org. Chem., 1968, 33, 3073 CrossRef CAS.
  11. (a) J. March, Advanced Organic Chemistry, Wiley, New York, 4th edn., 1992, ch. 9, and references therein Search PubMed; (b) T. H. Lowry and K. S. Richardson, Mechanism and Theory in Organic Chemistry, Harper & Row, New York, 3rd edn., 1987, p. 153 Search PubMed.
  12. C. Hansch, A. Leo and R. W. Taft, Chem. Rev., 1991, 91, 165 CrossRef CAS.
  13. (a) T. N. Hall, Tetrahedron, 1963, 19(Suppl. 1), 115 CAS; (b) T. N. Hall, J. Org. Chem., 1964, 29, 3587 CAS.
  14. V. K. Krylov and I. V. Tselinskii, Org. React. (USSR), 1970, 7, 33 Search PubMed.
  15. (a) H. S. Booth and D. R. Martin, Boron Trifluoride and Its Derivatives, Wiley, New York, 1949, pp. 176–182 Search PubMed; (b) A. V. Topchiev, S. V. Zavgorodnii and Ya. M. Paushkin, Boron Fluoride and Its Compounds as Catalysts in Organic Chemistry, Pergamon Press, New York, 1959, ch. 7 Search PubMed.
  16. H. G. Adolph, USP 3 962 349/ 1976.
  17. (a) R. R. McGuire, R. E. Cochoy and S. A. Shackelford, USP 4 424 398/ 1984; (b) R. E. Cochoy, R. R. McGuire and S. A. Shackelford, J. Org. Chem., 1990, 55, 1401 CrossRef CAS; (c) S. A. Shackelford, R. R. McGuire and R. E. Cochoy, J. Org. Chem., 1992, 57, 2950 CrossRef CAS; (d) R. R. McGuire, J. L. Pflug, M. H. Rakowsky, S. A. Shackelford and A. A. Shaffer, Heterocycles, 1994, 38, 1979 CAS.
  18. H. Feuer, G. Leston, R. Miller and A. T. Nielsen, J. Org. Chem., 1963, 28, 339 CAS.
  19. (a) M. Eisenberg and D. D. DesMarteau, Inorg. Nucl. Chem. Lett., 1970, 6, 29 Search PubMed; (b) K. Seppelt and D. Lentz, Prog. Inorg. Chem., 1982, 29, 167 CAS.
  20. S. A. Shackelford, R. R. McGuire and J. L. Pflug, Tetrahedron Lett., 1977, 363 CrossRef CAS.
  21. R. A. Hildreth, M. L. Druelinger and S. A. Shackelford, Tetrahedron Lett., 1982, 1059 CrossRef CAS In this paper, product VI is incorrectly displayed; it should be 3-exo-acetamido-2-endo-fluoronorbornane.
  22. Reactions based on alcohols 1b and 1d–g were conducted at the University of Southern Colorado in a time period without access to a suitable spectrometer to provide detailed NMR characterizations of all products. Interpretations based on our reported GC–MS data for the products derived from these alcohols are completely consistent with the fully characterized reactions using 1a1 and 1c, reported herein.
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