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Synthetic approach towards cuparene-type sesquiterpenes via highly regioselective epoxide opening under acid catalysis

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Abstract

Obtaining cuparene-type sesquiterpenes is a significant synthetic challenge mainly because of the construction of the sterically hindered quaternary centres. We report herein the successful construction of such quaternary moiety by a highly regioselective opening of (+/−)-2,5-dimethoxy-4-methyl-α-methylstyrene oxide by the acetone silyl enol ether catalysed by Lewis acid. Additionally, an efficient epoxidation of the highly activated 2,5-dimethoxy-4-methyl-α-styrene was accomplished by modifications on the dioxirane-promoted epoxidation protocol. Intensive optimisations for both key steps allowed the synthesis of the desired branched homo-aldol adduct, proposed as a key intermediate for a short synthetic alternative towards enokipodins.

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References

  1. Wasser SP, Weis AL (1999) Crit Rev Immunol 19:65

    CAS  PubMed  Google Scholar 

  2. Wang H, Ng TB, Ooi VE (1998) Mycol Res 102:897

    Article  CAS  Google Scholar 

  3. Yaoita Y, Matsuki K, Iijima T, Nakano S, Kakuda R, Machida K, Kikushi M (1998) Chem Pharm Bull 46:944

    Article  CAS  Google Scholar 

  4. Hirai Y, Ikeda M, Murayama T, Ohata T (1998) Biosci Biotechnol Biochem 62:1364

    Article  CAS  PubMed  Google Scholar 

  5. Ishikawa NK, Fukushi Y, Yamaji K, Tahara S, Takahashi K (2001) J Nat Prod 64:932

    Article  CAS  PubMed  Google Scholar 

  6. Ishikawa NK, Yamaji K, Tahara S, Fukushi Y, Takahashi K (2000) Phytochemistry 54:777

    Article  CAS  PubMed  Google Scholar 

  7. Ishikawa NK, Yamaji K, Ishimoto H, Miura K, Fukushi Y, Takahashi K (2005) Mycoscience 46:39

    Article  CAS  Google Scholar 

  8. Melo MR, Paccola-Meirelles LD, Faria TJ, Ishikawa NK (2009) Mycoscience 50:78

    Article  CAS  Google Scholar 

  9. Nascimento CB, Macedo FC Jr (2014) Quim Nova 8:1377

    Google Scholar 

  10. Srikrishna A, Srinivasa Rao M (2004) Synlett 2004:374

    Article  CAS  Google Scholar 

  11. Srikrishna A, Lakshini BV, Ravikumar PC (2006) Tetrahedron Lett 47:1277

    Article  CAS  Google Scholar 

  12. Secci F, Frongia A, Olliver J, Piras PP (2007) Synthesis 2007:999

    Article  CAS  Google Scholar 

  13. Srikrishna A, Srinivasa Rao M (2010) Indian J Chem Sect B 49:1363

    Google Scholar 

  14. Kuwahara S, Saito M (2004) Tetrahedron Lett 45:5047

    Article  CAS  Google Scholar 

  15. Kuwahara S, Saito M (2005) Biosci Biotechnol Biochem 69:374

    Article  PubMed  Google Scholar 

  16. Yoshida M, Shoji Y, Shishido K (2009) Org Lett 11:1441

    Article  CAS  PubMed  Google Scholar 

  17. Luján-Montelongo JA, Ávila-Zárraga JG (2010) Tetrahedron Lett 51:2232

    Article  CAS  Google Scholar 

  18. Leboeuf D, Wright CM, Frontier AJ (2013) Chem Eur J 19:4835

    Article  CAS  PubMed  Google Scholar 

  19. Hodgson DM, Chung YK, Nuzzo I, Freixas G, Kulikiewicz KK, Cleator E, Paris JM (2007) J Am Chem Soc 129:4456

    Article  CAS  PubMed  Google Scholar 

  20. Lalić G, Petrovski Z, Galonić D, Matović R, Saičić RN (2000) Tetrahedron Lett 41:763

    Article  Google Scholar 

  21. Lalić G, Petrovski Z, Galonić D, Matović R, Saičić RN (2001) Tetrahedron 57:583

    Article  Google Scholar 

  22. Lalić G, Petrovski Z, Galonić D, Matović R, Saičić RN (2002) J Serbian Chem Soc 67:221

    Article  Google Scholar 

  23. Curci R, Fiorentino M, Serio MR (1984) J Chem Soc Chem Commun 1984:155

    Article  Google Scholar 

  24. Wang Z, Tu Y, Frohn M, Shi Y (1997) J Org Chem 62:2328

    Article  CAS  PubMed  Google Scholar 

  25. Fuganti C, Serra SJ (2000) J Chem Soc Perkin Trans 1:3758

    Article  Google Scholar 

  26. Macedo FC Jr, Andrei CC, Campiom D, Ishikawa NK (2011) Tetrahedron Lett 52:1612

    Article  CAS  Google Scholar 

  27. Berens U, Scharf HD (1995) J Org Chem 60:5127

    Article  CAS  Google Scholar 

  28. Serra S (2011) Tetrahedron Asymmetry 22:619

    Article  CAS  Google Scholar 

  29. Sudalai A, Krishna Rao GS (1989) Indian J Chem 28B:720

    Google Scholar 

  30. Delgado A, Granados R, Mauleon D, Soucheiron I, Feliz M (1985) Can J Chem 63:3186

    Article  CAS  Google Scholar 

  31. Lecornué F, Paugam R, Oliver J (2005) Eur J Org Chem 2005:2589

    Article  CAS  Google Scholar 

  32. Meinwald J, Labana SS, Chadha MS (1963) J Am Chem Soc 85:582

    Article  CAS  Google Scholar 

  33. Mukaiyama T, Banno K, Narasaka K (1974) J Am Chem Soc 96:7503

    Article  CAS  Google Scholar 

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Acknowledgements

C. B. N. are recipients of scholarships from CAPES. We thank ‘Laboratório Multiusuário de Espectroscopia’ (SPEC)-UEL for acquisition of the NMR spectra.

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Authors and Affiliations

  1. Departamento de Química, Universidade Estadual de Londrina, Londrina, Brazil

    Camila B. Nascimento, Leandro A. Avelar, Danilo C. Arantes & Fernando Macedo Jr.

  2. Instituto Nacional de Pesquisas da Amazônia (INPA), Manaus, AM, Brazil

    Noêmia K. Ishikawa

Authors
  1. Camila B. Nascimento
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  2. Leandro A. Avelar
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  3. Danilo C. Arantes
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  4. Noêmia K. Ishikawa
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  5. Fernando Macedo Jr.
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Corresponding author

Correspondence to Fernando Macedo Jr..

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Nascimento, C.B., Avelar, L.A., Arantes, D.C. et al. Synthetic approach towards cuparene-type sesquiterpenes via highly regioselective epoxide opening under acid catalysis. Monatsh Chem 149, 1899–1904 (2018). https://doi.org/10.1007/s00706-018-2199-6

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  • DOI: https://doi.org/10.1007/s00706-018-2199-6

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