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Synlett 2009(2): 233-236  
DOI: 10.1055/s-0028-1087519
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Application of an Intramolecular Stetter Reaction to Access trans,syn,trans-Fused Pyrans

Christopher S. P. McErlean*a, Anthony C. Willisb
a School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia
Fax: +61(2)93513329; e-Mail: C.McErlean@chem.usyd.edu.au;
b Research School of Chemistry, The Australian National University, Canberra, ACT 0200, Australia
Further Information

Publication History

Received 19 September 2008
Publication Date:
15 January 2009 (online)

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Abstract

The use of a commercially available thiazolium salt facilitated an intramolecular Stetter reaction between an aliphatic aldehyde and an acrylate unit, which delivered a trans,syn-fused bicyclic pyranone in high yield as a single diastereomer. The pyranone was used to synthesize a trans,syn,trans-fused polycyclic ether array and was ring expanded to give the corresponding oxepanone.

Key words

carbenes - diastereoselectivity - fused-ring systems - ring closure - umpolung

    References and Notes

  • 1a Stetter H. Kuhlmann H. Angew. Chem., Int. Ed. Engl.  1974,  13:  539 
    Google Scholar
  • 1b Stetter H. Angew. Chem., Int. Ed. Engl.  1976,  15:  639 
    Google Scholar
  • 1c Stetter H. Org. React.  1991,  40:  407 
    Google Scholar
  • 2 Seebach D. Angew. Chem., Int. Ed. Engl.  1979,  18:  239 
    Google Scholar
  • 3 Breslow R. J. Am. Chem. Soc.  1958,  80:  3719 
    Google Scholar
  • 4 Ciganek E. Synthesis  1995,  1311 
    Article in Thieme ConnectGoogle Scholar
  • 5 Trost BM. Shuey CD. DiNinno F. McElain SS.
    J. Am. Chem. Soc.  1979,  101:  1284 
    CrossrefGoogle Scholar
  • 6a Enders D. Breuer K. Runsink J. Teles JH. Helv. Chim. Acta  1996,  79:  1899 
    Google Scholar
  • 6b Enders D. Balensiefer T. Acc. Chem. Res.  2004,  37:  534 
    Google Scholar
  • 7 Rovis T. Kerr MS. Synlett  2003,  1934 
    Article in Thieme ConnectGoogle Scholar
  • 8a Read de Alaniz J. Kerr MS. Moore JL. Rovis T.
    J. Org. Chem.  2008,  73:  2033 
    Google Scholar
  • 8b Kerr MS. Read de Alaniz J. Rovis T. J. Am. Chem. Soc.  2002,  124:  10298 
    Google Scholar
  • 8c Kerr MS. Rovis T. J. Am. Chem. Soc.  2004,  126:  8876 
    Google Scholar
  • 8d Rovis T. Read de Alaniz J. J. Am. Chem. Soc.  2005,  127:  6284 
    Google Scholar
  • 8e Rovis T. Moore JL. Kerr MS. Tetrahedron  2006,  62:  11477 
    Google Scholar
  • 8f Kerr MS. Read de Alaniz J. Rovis T. J. Org. Chem.  2005,  70:  5725 
    Google Scholar
  • 9a Johnson JS. Angew. Chem. Int. Ed.  2004,  43:  1326 
    Google Scholar
  • 9b Johnson JS. Curr. Opin. Drug Discovery Dev.  2007,  10:  691 
    Google Scholar
  • 10a Mattson AE. Bharadwaj AR. Scheidt KA. J. Am. Chem. Soc.  2004,  126:  2314 
    Google Scholar
  • 10b Mattson AE. Bharawaj AR. Zuhl AM. Scheidt KA. J. Org. Chem.  2006,  71:  5715 
    Google Scholar
  • 11 Enders D. Niemeier O. Henseler A. Chem. Rev.  2007,  107:  5606 
    Google Scholar
  • 12a Nicolaou KC. Tang Y. Wang J. Chem. Commun.  2007,  1922 
    Google Scholar
  • 12b Nicolaou KC. Pappo D. Tsang KY. Gibe R. Chen DY.-K. Angew. Chem. Int. Ed.  2008,  47:  944 
    Google Scholar
  • For polycyclic ethers, see:
  • 13a Bowden B. Toxin Rev.  2006,  25:  137 
    Google Scholar
  • 13b Inoue M. Chem. Rev.  2005,  105:  4379 
    Google Scholar
  • 13c Lin Y.-Y. Risk M. Ray SM. Van Engen D. Clardy J. Golik J. James JC. Nakanishi K. J. Am. Chem. Soc.  1981,  103:  6773 
    Google Scholar
  • 13d Matsuo G. Kawamura K. Hori N. Matsukura H. Nakata T. J. Am. Chem. Soc.  2004,  126:  14374 
    Google Scholar
  • 13e Nakata T. Chem. Rev.  2005,  105:  4314 
    Google Scholar
  • 13f For iterative approaches to polycyclic ethers, see: Sasaki M. Top. Heterocycl. Chem.  2006,  5:  149 
    Google Scholar
  • 13g Canoa P. Pérez M. Covelo B. Gómeza G. Fall Y. Tetrahedron Lett.  2007,  48:  3441 
    Google Scholar
  • 13h Kimura T. Nakata T. Tetrahedron Lett.  2007,  48:  43 
    Google Scholar
  • 13i Kimber MC. Robertson J. McErlean CSP. Wilson C. Clark JS. Angew. Chem. Int. Ed.  2005,  44:  6157 
    Google Scholar
  • 13j Kadota I. Yamamoto Y. Acc. Chem. Res.  2005,  38:  423 ; and references therein
    Google Scholar
  • 13k Trost BM. Rhee YH. Org. Lett.  2004,  6:  4311 
    Google Scholar
  • 13l For approaches utilizing acrylate esters, see: Marmsater FP. West FG. Chem. Eur. J.  2002,  8:  4346 ; and references therein
    Google Scholar
  • 13m Evans PA. Roseman JD. Garber LT. J. Org. Chem.  1996,  61:  4880 
    Google Scholar
  • 13n Hori N. Matsukura H. Matsuo G. Nakata T. Tetrahedron Lett.  1999,  40:  2811 
    Google Scholar
  • 13o Hori N. Matsukura H. Matsuo G. Nakata T. Tetrahedron  2002,  58:  1853 
    Google Scholar
  • 14 Hegedus LS. McKearin JM. J. Am. Chem. Soc.  1982,  104:  2444 
    Google Scholar
  • 15a Winterfeldt E. Chem. Ber.  1964,  97:  1952 
    Google Scholar
  • 15b Hori N. Matsukura H. Matsuo G. Nakata T. Tetrahedron Lett.  1999,  40:  2811 
    Google Scholar
  • 16 Betancort JM. Martín VS. Padrón JM. Palazón JM. Ramírez MA. Soler MA. J. Org. Chem.  1997,  62:  4570 
    CrossrefGoogle Scholar
  • 18 Mori Y. Yaegashi K. Furukawa H. J. Am. Chem. Soc.  1996,  118:  8158 
    CrossrefGoogle Scholar
  • 19a

    For the synthesis of compound 13 see Supporting Information.

  • 19b

    CCDC 702838 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

  • 20a

    A crystalline p-bromobenzoate derivative of a similar fused bicyclic system has been reported. [²0b] Therefore, alcohol 12 was converted into the corresponding p-bromo-benzoate but that compound failed to provide crystals suitable for X-ray crystallographic analysis.

  • 20b Nicolaou KC. Prasad CVC. Somers PK. Hwang C.-K. J. Am. Chem. Soc.  1989,  111:  5330 
    Google Scholar
  • 21a Shioiri T. Hashimoto N. Aoyama T. Tetrahedron Lett.  1980,  21:  4619 
    Google Scholar
  • 21b Mori Y. Yaegashi K. Furukawa H.
    J. Am. Chem. Soc.  1997,  119:  4557 
    Google Scholar
  • 21c Mori Y. Nogami K. Hayashi H. Noyori R. J. Org. Chem.  2003,  68:  9050 
    Google Scholar
17

Synthesis of Compound 8
To a solution of aldehyde 7 (58 mg, 0.24 mmol) in THF (2 mL) was added thiazolium salt 11 (90 mg, 0.36 mmol) and DBU (54 µL, 0.36 mmol). The mixture was stirred under reflux for 16 h, poured onto H2O (30 mL), and extracted with EtOAc (4 × 10 mL). The combined organic phases were dried over Na2SO4, the solvent was evaporated, and the residue was subjected to flash chromatography, eluting with 10% EtOAc in hexanes, to give 8 (57 mg, 98%) as a clear oil. IR (CHCl3): νmax = 3093, 2977, 2931, 1735, 1720, 1450, 1396, 1288, 1172, 1103, 1026 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 4.29 (1 H, dd, J = 6.0, 5.7 Hz), 4.14 (2 H, q, J = 7.2 Hz), 3.36 (1 H, ddd, J = 9.9, 9.9, 4.5 Hz), 2.87 (1 H, dd, J = 16.5, 5.4 Hz), 2.62 (1 H, dd, J = 16.5, 6.3 Hz), 2.55 (1 H, dd, J = 15.5, 4.5 Hz), 2.15 (1 H, dd, J = 15.5, 12.3 Hz), 2.05-1.99 (1 H, m), 1.85-1.62 (4 H, m), 1.37-1.06 (4 H, m), 1.25 (3 H, t, J = 7.2 Hz). ¹³C NMR (75.4 MHz, CDCl3): δ = 206.6 (C), 171.0 (C), 80.5 (CH), 79.7 (CH), 60.7 (CH2), 45.1 (CH2), 42.9 (CH), 35.3 (CH2), 32.0 (CH2), 31.7 (CH2), 24.9 (CH2), 24.6 (CH2), 14.2 (CH3). HRMS: m/z calcd for C13H21O4 [M + H+]: 241.14344; found: 241.14383.