View PDF Version
 
DOI: 10.1039/A806735J (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1998, 3957-3966

Simple synthesis of allobetulin, 28-oxyallobetulin and related biomarkers from betulin and betulinic acid catalysed by solid acids

(Note: The full text of this document is currently only available in the PDF Version )

Tong-Shuang Li, Jian-Xin Wang and Xue-Jing Zheng

Abstract

Allobetulin (3a) and allobetulin acetate (3b) were efficiently prepared in excellent yield from betulin (2a) and betulin 3-acetate (2b) catalysed by a number of solid acids in refluxing dichloromethane. Sulfuric acid on silica, montmorillonite clays (both K10 and KSF), kaolinite, bleaching clay and toluene-p-sulfonic acid on silica are efficient catalysts for these conversions. Similarly, 28-oxyallobetulin (3c) and 28-oxyallobetulin acetate (3d) were obtained in good and excellent yield from betulinic acid (2c) and betulinic acid acetate (2d) respectively catalysed by montmorillonite K10. Two allobetulin related biomarkers, 19β,28-epoxy-A-neo-18α-olean-3(5)-ene (4a) and A-neo-18α-olean-3(5)-en-28→19β-olide (4b) were synthesised either from 3a and 3c or directly from 2a and 2c in refluxing benzene or cyclohexane catalysed by montmorillonite K10. Two other biomarkers, 19β,28-epoxy-18α-olean-2-ene (10a) and 18α-olean-2-en-28→19β-olide (10b) were also synthesised based on the above transformations. The direct formation of allobetulane related biomarkers from natural betulin 2a and betulinic acid 2c catalysed by clay mineral (montmorillonite) is of great geochemical interest.

References

  1. For example: M. M. O'Connell, M. D. Bentley, C. S. Campbell and B. J. W. Cole, Phytochemistry, 1988, 27, 2715 Search PubMed; R. Ekman, Holzforschung, 1983, 37, 205 CrossRef.
  2. F. N. Lugemwa, F.-Y. Huang, M. D. Bentley, M. J. Mendel and A. R. Alford, J. Agric. Food Chem., 1990, 38, 493 CrossRef CAS.
  3. J. Klinot, M. Budesinsky and J. Svetly, Collect. Czech. Chem. Commun., 1990, 55, 766 CAS.
  4. L. E. Odinokova, M. V. Denisenko, V. A. Denisenko and N. I. Uvarova, Khim. Pr. Soedin., 1988, 212 Search PubMed.
  5. T. A. Hase, E. Suokas and A. Weckman, Synth. Commun., 1981, 11, 489 CAS.
  6. G. Berti, F. Bottari, A. Marsili and I. Morelli, Tetrahedron, 1971, 27, 2143 CrossRef CAS.
  7. V. G. Platanov, A. D. Zorina, M. A. Gordon, N. P. Chizhov, L. V. Balykina, Yu. D. Milhailov, D. R. Ivanen, T. K. Kvi and A. G. Shavva, Khim.-Farm. Zh., 1995, 29, 42 Search PubMed.
  8. A. White, E. J. Horsington, N. Nedjar, T. M. Peakman and J. A. Curiale, Tetrahedron Lett., 1998, 39, 3031 CrossRef CAS.
  9. V. Jarolim, K. Hejno, M. Streibl, M. Horak and F. Sorm, Collect. Czech. Chem. Commun., 1961, 26, 459 CAS.
  10. V. Jarolim, K. Hejno and F. Sorm, Collect. Czech. Chem. Commun., 1963, 28, 2443 CAS.
  11. D. H. R. Barton, W. Carruthers and K. H. Overton, J. Chem. Soc., 1956, 788 Search PubMed.
  12. H. Schulze and K. Pieroh, Chem. Ber., 1922, 55, 2332 Search PubMed.
  13. O. Dischendorfer, Monatsh. Chem., 1923, 44, 123 CAS.
  14. D. H. R. Barton and J. J. Holness, J. Chem. Soc., 1952, 78 RSC.
  15. W. Lawrie, J. McLean and G. R. Taylor, J. Chem. Soc., 1960, 4303 RSC.
  16. S. G. Errington, E. L. Ghisalbert and P. R. Jefferies, Aust. J. Chem., 1976, 29, 1809 CAS.
  17. E. Linkowska, Pol. J. Chem., 1994, 68, 875 (Chem. Abstr., 1994, 121, 23 1096) CAS.
  18. S. C. Pakrashi and T. B. Samanta, Indian J. Chem., 1969, 7, 522 Search PubMed.
  19. S. C. Pakrashi, J. Bhattacharyya, S. Mookerjee and T. B. Samanta, Phytochemistry, 1968, 7, 461 CrossRef CAS.
  20. A. Cornelis and P. Laszlo, Synlett, 1994, 155 CrossRef CAS; T.-S. Li and T.-S. Jin, Youji Huaxue, 1996, 16, 385 Search PubMed; D. Ponde, H. B. Borate, A. Sudalai, T. Ravindranathan and V. H. Deshpande, Tetrahedron Lett., 1996, 37, 4605 CrossRef CAS.
  21. T.-S. Li, Z.-H. Zhang and C.-G. Fu, Tetrahedron Lett., 1997, 38, 3285 CrossRef CAS; A.-X. Li, T.-S. Li and T.-H. Ding, Chem. Commun., 1998, 1389 RSC.
  22. T.-S. Li, Y.-T. Yang and Y.-L. Li, J. Chem. Res. (S), 1993, 28 Search PubMed; X. Chen, F.-J. Nan, S.-C. Shao, L.-Y. Min, T.-S. Li and Y.-L. Li, Indian J. Chem., Sect. B, 1993, 32, 772; T.-S. Li, J. Hebei Univ., Nat. Sci. Ed., 1996, 16, 71 Search PubMed.
  23. Y.-C. Xu, A. Bizuneh and C. Walker, J. Org. Chem., 1996, 61, 9086 CrossRef CAS.
  24. F. Chavez, S. Suarez and M. Diaz, Synth. Commun., 1994, 24, 2325 CAS.
  25. G. Blay, M. L. Cardona, M. B. Garcia and J. R. Pedro, Synthesis, 1989, 438 CrossRef CAS.
  26. T.-S. Jin, G.-Y. Du, Z.-H. Zhang and T.-S. Li, Synth. Commun., 1997, 27, 2261.
  27. G. R. Pettit, B. Green and W. J. Bowyer, J. Org. Chem., 1961, 26, 2879 CrossRef CAS.
  28. T.-S. Li, J.-T. Li and H.-Z. Li, J. Chromatogr., A, 1995, 715, 372 CrossRef CAS.
  29. H. L. Ten Haven, T. M. Peakman and J. Rullkotter, Geochim. Cosmochim. Acta, 1992, 56, 1993 CAS.
  30. I. R. Hill, G. W. Smith and E. V. Whitehead, J. Inst. Pet., 1970, 56, 127 Search PubMed.
  31. J. H. Partterson, Chem. Geol., 1988, 68, 207 CAS; J. F. Banfield, B. F. Jones and D. R. Veblen, Geochim. Cosmochim. Acta, 1991, 55, 2795 CAS.
  32. I. Rubinstein, O. Sieskind and P. Albrecht, J. Chem. Soc., Perkin Trans. 1, 1975, 1833 RSC; O. Sieskind, G. Joly and P. Albrecht, Geochim. Cosmochim. Acta, 1979, 43, 1675 CrossRef CAS.
  33. D. S. H. L. Kim, Z.-D. Chen, V. T. Nguyen, J. M. Pezzuto, S.-X. Qiu and Z.-Z. Liu, Synth. Commun., 1997, 27, 1607 CrossRef CAS.
  34. T. Fujioka, Y. Kashiwada, R. E. Kilkuskie, L. M. Cosentino, L. B. Ballas, J. B. Jiang, W. P. Janzen, I. S. Chen and K. H. Lee, J. Nat. Prod., 1994, 57, 243 CrossRef CAS.
  35. J. Klinot and A. Vystrcil, Collect. Czech. Chem. Commun., 1964, 29, 516 CAS.