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Synthesis 2008(21): 3516-3524  
DOI: 10.1055/s-0028-1083180
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Straightforward Synthesis of 2,3,4,5-Tetrasubstituted Tetrahydrofuran Derivatives

Ana Aljarilla, Joaquín Plumet*
Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain
Fax: +34(913)944103; e-Mail: plumety@quim.ucm.es;
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Publication History

Received 11 June 2008
Publication Date:
16 October 2008 (online)

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Abstract

A concise synthesis of 2,3,4,5-tetrasubstituted tetrahydrofurans starting from furan via 7-oxabicyclo[2.2.1]hept-5-ene-2,3-diol (2,3-dihydroxy-7-oxanorbornene) derivatives is reported. The key step of these transformations was the sequence ring-opening metathesis-cross metathesis (ROM-CM) reactions of the oxa­bicyclic compounds in the presence of ethylene and using commercially available 2nd generation Hoveyda-Grubbs catalyst.

Key words

metathesis - tetrahydrofurans - Hoveyda-Grubbs catalyst - oxabicyclic compounds

    References

  • See, for instance, the following reviews:
  • 1a Bermejo A. Figadere B. Zafra-Polo MC. Barrachina I. Estornell E. Cortés D. Nat. Prod. Rep.  2005,  22:  269 
    Google Scholar
  • 1b For a review on the synthesis of the tetrahydrofuran ring core of some of these compounds, see: Hu TS. Wu YL. Yao ZJ. Med. Chem. Bioact. Nat. Prod.  2006,  399 
    Google Scholar
  • 1c Maezaki N. Kojima N. Tanaka T. Synlett  2006,  993 
    Google Scholar
  • 2 Review: Faul MM. Huff BE. Chem. Rev.  2000,  100:  2407 
    CrossrefGoogle Scholar
  • 3 Review: Saleem M. Kim HJ. Ali MS. Lee YS. Nat. Prod. Rep.  2005,  22:  696 
    CrossrefPubMedGoogle Scholar
  • 4 Review: Kang EJ. Lee E. Chem. Rev.  2005,  105:  4348 
    CrossrefPubMedGoogle Scholar
  • 5 For instance, furan fatty acids (F-acids), for a review see: Spiteller G. Lipids  2005,  40:  755; and references therein 
    CrossrefGoogle Scholar
  • For a general review on the synthesis of tetrahydrofurans covering the literature published between 1993 and 2005 see:
  • 6a For selected reviews on specific synthetic methods prior to this reference, see: Wolfe JP. Hay MB. Tetrahedron  2007,  63:  261 
    Google Scholar
  • 6b Martius da Silva F. Jones J. de Mattos CS. Curr. Org. Synth.  2005,  2:  393 
    Google Scholar
  • 6c Padwa A. J. Organomet. Chem.  2005,  690:  5525 
    Google Scholar
  • 6d Lee E. Pure Appl. Chem.  2005,  77:  2073 
    Google Scholar
  • 6e Wolfe JP. Eur. J. Org. Chem.  2007,  571 
    Google Scholar
  • 6f Piccialli V. Synthesis  2007,  2585 
    Google Scholar
  • See ref. 6a. For other selected, more recent reports concerning the synthesis of tetrasubstituted tetrahydrofurans, see:
  • 7a Akindele T. Mardsen SP. Cumming JG. Org. Lett.  2005,  7:  3685 
    Google Scholar
  • 7b Kumar V. Gauniyal HM. Shaw AK. Tetrahedron: Asymmetry  2007,  18:  2069 
    Google Scholar
  • 7c Hannesian S. Reddy GJ. Synlett  2007,  475 
    Google Scholar
  • 7d Kollmann S. Froelich R. Hoppe D. Synthesis  2007,  883 
    Google Scholar
  • 7e Colobert F. Choppin S. Ferreiro-Mederos L. Obringer M. Luengo-Arratta S. Urbano A. Carreño MC. Org. Lett.  2007,  9:  4451 
    Google Scholar
  • 7f Nasveschuck CG. Rovis T. J. Org. Chem.  2008,  73:  612 
    Google Scholar
  • For a general treatise, see:
  • 8a See also: Handbook of Metathesis   Grubbs RH. Wiley-VCH; Weinheim: 2003. see in particular Vol. 2: Applications in Organic Synthesis
    Google Scholar
  • 8b For further selected reviews covering the synthesis of heterocyclic compounds using metathetical reactions, see: Grubbs RH. Trnka TM. Ruthenium-Catalyzed Olefin Metathesis, In Ruthenium in Organic Synthesis   Murahashi SI. Wiley-VCH; Weinheim: 2006.  Chap. 6.
    Google Scholar
  • 8c Felpin FX. Lebeton J. Eur. J. Org. Chem.  2003,  3693 
    Google Scholar
  • 8d McReynolds MD. Dougherty JM. Hanson PR. Chem. Rev.  2004,  104:  2239 
    Google Scholar
  • 8e Walters MA. Recent Advances in the Synthesis of Heterocycles via Ring-Closing Metathesis, In Progress in Heterocyclic Chemistry   Chap. 1, Vol. 15:  Gribble GW. Joule JA. Pergamon; Oxford: 2003. 
    Google Scholar
  • 8f Deiters A. Martin SF. Chem. Rev.  2004,  104:  2199 
    Google Scholar
  • 8g Martin SF. Pure Appl. Chem.  2005,  77:  1207 
    Google Scholar
  • 8h Schmid B. Hermanns J. Curr. Org. Chem.  2006,  10:  1363 
    Google Scholar
  • 8i Clark JS. Chem. Commun.  2006,  3571 
    Google Scholar
  • 8j Arisawa M. Nishida A. Nakagama M. J. Organomet. Chem.  2006,  691:  5109 
    Google Scholar
  • 8k Chattopadhyay SK. Karmakar S. Biswas T. Majumdar KL. Rahman H. Roy B. Tetrahedron  2007,  63:  3919 
    Google Scholar
  • 10 Louis J. Bielawski CW. Grubbs RH. J. Am. Chem. Soc.  2001,  123:  11312 
    CrossrefGoogle Scholar
  • Concurrent Tandem Catalysis methodology involves the cooperative action of two or more catalytic cycles in a single reactor. For general reviews, see:
  • 11a Ajamanian A. Gleason JL. Angew. Chem. Int. Ed.  2004,  43:  3754 
    Google Scholar
  • 11b Wasilke JC. Obrey SJ. Baker RT. Bazan C. Chem. Rev.  2005,  105:  1001 
    Google Scholar
  • For selected reviews, see:
  • 12a Schmidt B. Eur. J. Org. Chem.  2004,  1865 
    Google Scholar
  • 12b Schmidt B. Pure Appl. Chem.  2006,  78:  469 
    Google Scholar
  • 12c Schmidt B. J. Mol. Catal. A: Chem.  2006,  254:  53 
    Google Scholar
  • 12d Dragutan V. Dragutan I. J. Organomet. Chem.  2006,  691:  5129 
    Google Scholar
  • 13a Review: Arjona O. Csákÿ AG. Plumet J. Eur. J. Org. Chem.  2003,  611 
    Google Scholar
  • 13b See also: Arjona O. Csákÿ AG. Plumet J. Synthesis  2000,  867 
    Google Scholar
  • 13c Connon SJ. Blechert S. Angew. Chem. Int. Ed.  2003,  42:  1900 
    Google Scholar
  • 14 Arjona O. Csákÿ AG. Murcia MC. Plumet J. J. Org. Chem.  1999,  64:  9379 
    Google Scholar
  • 15 Liu Z. Rainier JD. Org. Lett.  2005,  7:  131 
    CrossrefPubMedGoogle Scholar
  • 16a Schneider MF. Blechert S. Angew. Chem., Int. Ed. Engl.  1996,  35:  411 
    Google Scholar
  • 16b Schneider MF. Lucas N. Velder J. Blechert S. Angew. Chem., Int. Ed. Engl.  1997,  36:  257 
    Google Scholar
  • 17 Katayama H. Unishima H. Nishioka T. Wada C. Nagao M. Ozawa F. Angew. Chem. Int. Ed.  2000,  39:  4513 
    CrossrefPubMedGoogle Scholar
  • 18 Aljarilla A. Murcia MC. Plumet J. Synlett  2006,  831 
    Article in Thieme ConnectGoogle Scholar
  • 19a Kowarsli CR. Sarel S. J. Org. Chem.  1973,  38:  117 
    Google Scholar
  • 19b Baran A. Kazaz C. Secen H. Sütbeyaz Y. Tetrahedron  2003,  59:  3643 
    Google Scholar
  • 23 For a related transformation see: Chandler CL. Phillips AJ. Org. Lett.  2005,  7:  3493 
    CrossrefPubMedGoogle Scholar
  • For selected reviews see:
  • 24a Vogel P. Cossy J. Plumet J. Arjona O. Tetrahedron  1999,  55:  13521 
    Google Scholar
  • 24b Arjona O. Plumet J. Curr. Org. Chem.  2002,  6:  571 
    Google Scholar
  • 24c Lautens M. Fagnou K. Hiebert S. Acc. Chem. Res.  2003,  36:  48 
    Google Scholar
9

See ref. 6a, p 276 and references therein.

20

Enzymatic desymmetrization of diol 10 by transformation in enantiomerically enriched monoacetate (-)-14 (83%, 92% ee) in the presence of CCL has been reported in ref. 18. In the present report products with different values of ee (not determined) have been used.

21

Enzymatic desymmetrization of diol 11 has been carried out by transformation in enantiomerically enriched monoacetate (-)-23 (83%, 91% ee determined by ¹9F NMR spectroscopy of the corresponding Mosher’s ester derivative) using enzyme pig pancreatic lipase (PPL). Full details together with determination of the absolute configuration of compounds (-)-14 and (-)-23 are now in progress and will be reported in due course.

22

Commercially available 2nd generation Hoveyda-Grubbs catalyst shows efficiencies similar to 2nd generation Grubbs catalyst but with different substrate selectivity. Specifically it catalyzes RCM, ROM and CM reactions of electron-deficient substrates.