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Synlett 2010(18): 2747-2750  
DOI: 10.1055/s-0030-1258995
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of (+)-Sclareolide Based on a Cyclic Enol Ether Ring Contraction Induced by Peroxy Acids

Juan M. Castro, Sofía Salido, Adolfo Sánchez, Joaquín Altarejos*
Departamento de Química Inorgánica y Orgánica, Facultad de Ciencias Experimentales, Universidad de Jaén, 23071 Jaén, Spain
Fax: +34(953)211876; e-Mail: jaltare@ujaen.es;
Further Information

Publication History

Received 1 July 2010
Publication Date:
08 October 2010 (online)

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Abstract

(+)-Sclareolide has been synthesised from (+)-sclareol oxide in one step in high yield, by treatment with peroxy acids under very mild conditions. The reaction pathway does not follow the usual oxidative cleavage of the double bond of (+)-sclareol oxide, but the key intermediate is a five-membered ring hemiketal. The direct conversion of a six-membered cyclic enol ether into a γ-lactone is described for the first time.

Key words

cyclic enol ethers - γ-lactones - ring contraction - oxidative rearrangement - peroxy acids

    References and Notes

  • 1a First synthesis: Ruzicka L. Janot MM. Helv. Chim. Acta  1931,  14:  645 
    Search in Google Scholar
  • 1b Structure elucidation: Ruzicka L. Seidel CF. Engel LL. Helv. Chim. Acta  1942,  25:  621 
    Search in Google Scholar
  • 2 Kaneko H. Agric. Biol. Chem.  1971,  35:  1461 ; see also ref. 4
    CrossrefSearch in Google Scholar
  • 3a Stoll M. Hinder M. Helv. Chim. Acta  1950,  33:  1251 
    Search in Google Scholar
  • 3b Hinder M. Stoll M. Helv. Chim. Acta  1950,  1308 
  • 4 Ohloff G. In Fragrance Chemistry   Theimer ET. Academic Press; New York: 1982.  p.535 
  • 5 Fráter G. Bajgrowicz JA. Kraft P. Tetrahedron  1998,  54:  7633 
    CrossrefSearch in Google Scholar
  • 6 Schumacher JN. inventors; US  2,905,576.  ; Chem. Abstr. 1960, 54, 13261
  • 7 Rocabayera X, Figueras S, Segret R, and Piera E. inventors; WO  2008095534.  ; Chem. Abstr. 2008, 149, 266054
  • 8 Kim SH. Danilenko M. Kim TS. Br. J. Pharmacol.  2008,  155:  814 
    CrossrefSearch in Google Scholar
  • 9 Boggs A, Trias J, and Hecker S. inventors; WO  9,624,684.  ; Chem. Abstr. 1996, 125, 238654
  • 10 Nozoe S. Masuda J. Takahashi A. Kanou M. Tanaka K. Wakayama T. Koike N. Uchida T. Nagata T. Segawa T. Tanka S.   , ; Chem. Abstr. 1999, 131, 307085
  • 11 Subbiah V. inventors; WO  9,963,978.  ; Chem. Abstr. 1999, 132, 18772
  • 12 Gerke T, Sättler A, and Müllner S. inventors; WO  2002030385.  ; Chem. Abstr. 2002, 136, 299517
  • 13 Oh S. Jeong IH. Shin W.-S. Lee S. Bioorg. Med. Chem. Lett.  2003,  13:  2009 
    CrossrefSearch in Google Scholar
  • See, as examples, the syntheses from ambrein:
  • 14a Lederer E. Mercier D. Experientia  1947,  3:  188 
    Search in Google Scholar
  • And from labdanolic acid:
  • 14b de Pascual Teresa J. Urones JG. Montaña A. Basabe P. Tetrahedron Lett.  1985,  26:  5717 
    Search in Google Scholar
  • For recent papers, see:
  • 15a Upar KB. Mishra SJ. Nalawade SP. Singh SA. Khandare RP. Bhat SV. Tetrahedron: Asymmetry  2009,  20:  1637 
    Search in Google Scholar
  • 15b Snowden RL. Chemistry & Biodiversity  2008,  5:  958 
    Search in Google Scholar
  • Recent examples:
  • 16a Wei J, Wu Y, Shi X, and Zhang Y. inventors; CN  1,683,352.  ; Chem. Abstr. 2006, 145, 145522
  • 16b Igarashi K, Takizawa S, Higaki N, and Hagiwara H. inventors; JP  2007222110.  ; Chem. Abstr. 2007, 147, 299478
  • 17 Recent example: Álvarez-Manzaneda E. Chahboun R. Cabrera E. Álvarez E. Haïdour A. Ramos JM. Álvarez-Manzaneda R. Hmamouchi M. Es-Samti H. Chem. Commun.  2009,  592 
    Crossref
  • 18a Barrero AF. Altarejos J. Álvarez-Manzaneda EJ. Ramos JM. Salido S. J. Org. Chem.  1996,  61:  2215 
    Search in Google Scholar
  • 18b Barrero AF. Altarejos J. Álvarez-Manzaneda EJ. Ramos JM. Salido S. Tetrahedron  1993,  49:  6251 
    Search in Google Scholar
  • 18c Barrero AF. Altarejos J. Álvarez-Manzaneda EJ. Ramos JM. Salido S. Tetrahedron  1993,  49:  9525 
    Search in Google Scholar
  • 18d Barrero AF, Altarejos J, Álvarez-Manzaneda EJ, and Ramos JM. inventors; ES  2,044,780.  ; Chem. Abstr. 1994, 120, 299025
  • 18e Barrero AF, Altarejos J, and Salido S. inventors; ES  2,069,469.  ; Chem. Abstr. 1995, 123, 257086
  • 18f Barrero AF. Sánchez JF. Álvarez-Manzaneda EJ. Altarejos J. Muñoz M. Haïdour A. Tetrahedron  1994,  50:  6653 ; see also ref. 23b
    Search in Google Scholar
  • 19 Castro JM. Salido S. Altarejos J. Nogueras M. Sánchez A. Tetrahedron  2002,  58:  5941 
    CrossrefSearch in Google Scholar
  • 20a Cocker JD. Halsall TG. Bowers A. J. Chem. Soc.  1956,  4259 
  • 20b Cocker JD. Halsall TG. J. Chem. Soc.  1956,  4262 
  • 22 Gerke T, and Bruns K. inventors; DE  3,942,358.  ; Chem. Abstr. 1991, 115, 136446
  • Other oxidants normally yield mixtures of products 7 and 1 from 5/6. See as examples ref. 1a and:
  • 23a Zahra J.-P. Chauvet F. Coste-Manière I. Martres P. Perfetti P. Waegell B. Bull. Soc. Chim. Fr.  1997,  134:  1001 
    Search in Google Scholar
  • 23b Barrero AF. Álvarez-Manzaneda EJ. Altarejos J. Salido S. Ramos JM. Tetrahedron  1993,  49:  10405 
    Search in Google Scholar
  • 24a Urones JG. Basabe P. Marcos IS. Díez D. Sexmero MJ. Peral MH. Broughton HB. Tetrahedron  1992,  48:  10389 
    Search in Google Scholar
  • 24b González AG. Francisco CG. Freire R. Hernández R. Salazar JA. Suárez E. Tetrahedron Lett.  1976,  1897 
  • 25 One occurrence for compound 11 has been found in the literature: Giles JA. Schumacher JN. Tetrahedron  1961,  14:  246 ; compounds 8-10 have never been described before
    CrossrefSearch in Google Scholar
  • 26 Epimerization at C-8 of 1 is well known. See: Quideau S. Lebon M. Lamidey A.-M. Org. Lett.  2002,  4:  3975 
    CrossrefSearch in Google Scholar
  • 27 Peng S. Qing F.-L. Li Y.-Q. Hu C.-M. J. Org. Chem.  2000,  65:  694 
    CrossrefSearch in Google Scholar
  • 28 Li X. Wang F. Zhang H. Wang C. Song G. Synth. Commun.  1996,  26:  1613 
    CrossrefSearch in Google Scholar
  • 29 Castro JM, Salido S, Altarejos J, Nogueras M, and Sánchez A. inventors; ES  2,238,003.  ; Chem. Abstr. 2006, 145, 397666
  • 31 Dehal SS. Marples BA. Stretton RJ. Tetrahedron Lett.  1978,  25:  2183 
    Search in Google Scholar
  • 32a Hall SS. Chernoff HC. Chem. Ind.  1970,  27:  896 
    Search in Google Scholar
  • 32b Armstrong A. Ashraff C. Chung H. Murtagh L. Tetrahedron  2009,  65:  4490 ; note that the oxidative rearrangement of the 3,4-dihydropyrans described in these articles leads to tetrahydrofuranones, not to γ-lactones
    Search in Google Scholar
  • 33 Barton DHR. Parekh SI. Taylor DK. Tse C.-I. Tetrahedron Lett.  1994,  35:  5801 
    CrossrefSearch in Google Scholar
21

Acid traces present in commercial CDCl3 were capable of transforming 5 into 6 during the NMR experiments. Previous neutralisation of the deuterated solvent was necessary.

30

In ref. 23a, V is postulated in a related reaction mechanism.