Download PDF
Synlett 2005(10): 1575-1578  
DOI: 10.1055/s-2005-869865
LETTER
© Georg Thieme Verlag Stuttgart · New York

Acid-Mediated Highly Regioselective Oxidation of Substituted Furans: A Simple and Direct Entry to Substituted Butenolides

Juan P. Ceñala, Carlos R. Carrerasa, Carlos E. Tonna, Juan I. Padrónb, Miguel A. Ramírezb, David D. Díazb, Fernando García-Telladoc, Victor S. Martín*b
a INTEQUI-CONICET-Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700-San Luis, Argentina
b Instituto Universitario de Bioorgánica ‘Antonio González’, Universidad de La Laguna, Avda. Astrofísico Francisco Sánchez, 2, 38206 La Laguna, Tenerife, Canary Islands, Spain
Fax: +34(922)318571; e-Mail: vmartin@ull.es;
c Instituto de Productos Naturales y Agrobiología, Consejo Superior de Investigaciones Científicas, Avda. Astrofísico Francisco Sánchez, 3, 38206 La Laguna, Tenerife, Canary Islands, Spain
Further Information

Publication History

Received 11 February 2005
Publication Date:
07 June 2005 (online)

    Permissions and Reprints All articles of this category

Abstract

The scope and limitations of an expeditious synthesis of substituted butenolides from 3-substituted or 3,4-disubstituted furans is described. The entire process embodies a controlled oxidation of the furan core to a 2,5-dialkoxy-dihydrofuran intermediate and a regioselective acid-catalyzed hydrolysis to the butenolide ­derivative. 3-Substituted furans yield exclusively 2-substituted butenolides. Calculations studies provide substantiation of a proposed mechanism.

Key words

oxidation - furans - substituted butenolides

    References

  • 2a Turner WB. Fungal Metabolites   Academic Press; London: 1977.  p.284 
    CrossrefGoogle Scholar
  • 2b Rao YS. Chem. Rev.  1976,  76:  625 
    CrossrefGoogle Scholar
  • 2c Cavé A. Laprévote O. Laurens A. Lebeouf M. In Recent Advances in Phytochemistry   Downum KR. Romeo JT. Stafford HA. Plenum Press; New York: 1993. 
    CrossrefGoogle Scholar
  • 2d Cavé A. Figadère B. Laurens A. Cortes D. In Progress in the Chemistry of Natural Products   Vol. 70:  Herz W. Kirby GW. Moore RE. Steglich W. Tamm C. Springer; New York: 1997.  p.81 
    CrossrefGoogle Scholar
  • For known members of this family of metabolites, see for example:
  • 3a Zapf S. Anke T. Sterner O. Acta Chem. Scand.  1995,  49:  233 
    Google Scholar
  • 3b Scott LJ. Lamb HM. Drugs  1999,  58:  499 
    Google Scholar
  • 3c Tejedor D. García-Tellado F. Org. Prep. Proced. Int.  2004,  36:  35 
    Google Scholar
  • 3d Lorimer SD. Mawson SD. Perry NB. Weavers RT. Tetrahedron  1995,  51:  7287 
    Google Scholar
  • 3e Snieckus V. The Securinega Alkaloids, In The Alkaloids, Chemistry and Physiology   Vol. 14:  Manske RHF. Academic Press; New York: 1973.  p.425 
    Google Scholar
  • 3f Johnson HA. Oberlies NH. Alani FQ. Mclaughlin JL. In Biologically ActiveNatural Products: Pharmaceuticals   Cutler SJ. Cutler H. CRC Press; Boca Raton / USA: 1999.  p.173 
    Google Scholar
  • 3g Repke KRH. Megges R. Weiland J. Schön R. Angew. Chem., Int. Ed. Engl.  1995,  34:  282 
    Google Scholar
  • For a general review, see:
  • 4a Ma S. Acc. Chem. Res.  2003,  36:  701 
    CrossrefGoogle Scholar
  • 4b Bruckner R. Curr. Org. Chem.  2001,  5:  679 
    CrossrefGoogle Scholar
  • 4c Negishi E.-i. Kotora M. Tetrahedron  1997,  53:  6707 
    CrossrefGoogle Scholar
  • 4d For α-methylene-butenolides, see: Martín T. Martín VS. Rodríguez CM. Chim. Oggi  1996,  14:  15 
    CrossrefGoogle Scholar
  • 4e Knight DW. Contemp. Org. Synth.  1994,  1:  287 
    CrossrefGoogle Scholar
  • 5a Sargent MV. Dean FM. Furans and Benzoderivatives(ii): Reactivity, In Comprehensive Heterocyclic Chemistry   Vol. 4:  Katritzky AR. Rees CW. Pergamon; Oxford: 1984.  p.599 
    Google Scholar
  • 5b Heaney H. Ahn JS. Furans and Benzoderivatives: Reactivity, In Comprehensive Heterocyclic Chemistry   2nd ed., Vol. 2:  Katritzky AR. Rees CW. Scriven EF. Pergamon; Oxford: 1996.  p.297 
    Google Scholar
  • 5c Sargent MV. Cresp MT. Furans, In Comprehensive Organic Chemistry   Vol. 4:  Barton D. Ollis WD. Pergamon; Oxford: 1979.  p.693 
    Google Scholar
  • 6 Ley SV. Mahon M. J. Chem. Soc., Perkin Trans. 1  1983,  1379 
    CrossrefGoogle Scholar
  • 7 Hueso-Rodríguez JA. Rodríguez B. Tetrahedron  1989,  45:  1567 
    CrossrefGoogle Scholar
  • 8a Gopalakrishnan G. Singh NDP. Kasinath V. Krishnan MSR. Malathi R. Rajan SS. Tetrahedron Lett.  2001,  42:  6577 
    CrossrefGoogle Scholar
  • 8b

    In our hands, this reaction could not be accomplished with simple substituted furans.
    Crossref
  • 9a García C. Martín T. Martín VS. J. Org. Chem.  2001,  66:  1420 
    Google Scholar
  • 9b Díaz D. Martín VS. Org. Lett.  2000,  2:  335 
    Google Scholar
  • 9c Martín T. Rodríguez CM. Martín VS. J. Org. Chem.  1996,  61:  6450 
    Google Scholar
  • 9d Rodríguez CM. Martín T. Ramírez MA. Martín VS. J. Org. Chem.  1994,  59:  8081 
    Google Scholar
  • 9e Rodríguez CM. Martín T. Ramírez MA. Martín VS. J. Org. Chem.  1994,  59:  4461 
    Google Scholar
  • 10 Merino P. Franco S. Merchan FL. Tejero T. In Recent Advances in Synthetic Organic Chemistry   Vol. 3:  Pandalai SG. Transworld Research Network; Trivandum India: 2000.  p.65 ; and references cited therein
    Google Scholar
  • 11 Nedenskov P. Elming N. Nielsen JT. Clauson-Kaas N. Acta Chem. Scand.  1955,  9:  17 
    CrossrefGoogle Scholar
  • 12a For a review of 3-substituted furan synthesis, see: Hou XL. Cheung HY. Hon TY. Kwan PL. Lo TH. Tong SY. Wong HNC. Tetrahedron  1998,  54:  1955 
    CrossrefGoogle Scholar
  • 12b For a recent example of a direct synthesis, see: Barma DK. Kundu A. Baati R. Mioskowski C. Falck JR. Org. Lett.  2002,  4:  1387 
    CrossrefGoogle Scholar
  • 13 Calderon A. De March P. Font JMJ. Cheshire DR. Reynolds R. J. Org. Chem.  1987,  52:  4631 
    Google Scholar
  • 14 Tonn CE. Gianello JC. Giordano OS. An. Asoc. Quim. Argent.  1979,  67:  1 
    Google Scholar
  • 15a Ceñal JP. Giordano OS. Rossomando PC. Tonn CE. J. Nat. Prod.  1997,  60:  490 
    Google Scholar
  • 15b Tonn CE. Giordano OS. An. Asoc. Quim. Argent.  1980,  68:  237 
    Google Scholar
  • 16 Esquivel B. Hernández LM. Cárdenas J. Ramamoorthy TP. Rodríguez-Hahn L. Phytochemistry  1989,  28:  561 
    CrossrefGoogle Scholar
  • 17 Carreras CR. Rossomando PC. Giordano SO. Phytochemistry  1998,  48:  1031 
    CrossrefGoogle Scholar
  • 18a Bader RFW. In Atoms in Molecules: A Quantum Theory   Halpen J. Green MLH. The International Series of Monographs of Chemistry, Clarendon Press; Oxford: 1990.  p.1 
    CrossrefGoogle Scholar
  • 18b Bader RFW. Chem. Rev.  1991,  91:  893 
    CrossrefGoogle Scholar
  • 18c Popelier P. In Atoms in Molecules: An Introduction   Prentice Hall; Harlow: 2000.  p.1 
    CrossrefGoogle Scholar
  • 18d Gilespie RJ. Popelier PLA. In Chemical Bonding and Molecular Geometry: From Lewis to Electron Densities   Oxford University Press; Oxford: 2001.  p.134 
    CrossrefGoogle Scholar
  • 21 Danso-Danquah RE. Scott AI. Becker D. Tetrahedron  1993,  49:  8195 
    CrossrefGoogle Scholar
1

Instituto Canario de Investigación del Cáncer, www.icic.es.

19

Theoretical calculations details are available from the authors upon request.

20

Obtained by integration of the electronic density over the considered atomic basin.