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Synlett 2007(10): 1549-1552  
DOI: 10.1055/s-2007-982535
LETTER
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Total Synthesis of the Sesquiterpene (±)-Cameroonanol

Arndt W. Schmidt, Thomas Olpp, Sören Schmid, Sigrid Goutal, Anne Jäger, Hans-Joachim Knölker*
Department Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany
Fax: +49(351)46337030; e-Mail: hans-joachim.knoelker@tu-dresden.de;
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Publikationsverlauf

Received 12 April 2007
Publikationsdatum:
06. Juni 2007 (online)

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Abstract

We describe a stereoselective synthesis of the triquinane (±)-cameroonanol using the Lewis acid mediated [3+2] cyclo­addition of an allylsilane and a modified Fleming-Tamao oxidation as key steps.

Key words

cycloadditions - Lewis acids - silicon - stereoselective synthesis - terpenoids

    References and Notes

  • 1 Weyerstahl P. Marschall H. Seelmann I. Jakupovic J. Eur. J. Org. Chem.  1998,  1205 
  • 2 Fitjer L. Monzó-Oltra H. J. Org. Chem.  1993,  58:  6171 
    Suche in Google Scholar
  • 3a Davis CE. Duffy BC. Coates RM. Org. Lett.  2000,  2:  2717 
    Suche in Google Scholar
  • 3b Davis CE. Duffy BC. Coates RM. J. Org. Chem.  2003,  68:  6935 
    Suche in Google Scholar
  • 4 Mehta G. Srikrishna A. Chem. Rev.  1997,  97:  671 
    Suche in Google Scholar
  • 5a Knölker H.-J. Jones PG. Pannek J.-B. Synlett  1990,  429 
  • 5b Knölker H.-J. Foitzik N. Goesmann H. Graf R. Angew. Chem., Int. Ed. Engl.  1993,  32:  1081 
    Suche in Google Scholar
  • 5c Knölker H.-J. Jones PG. Graf R. Synlett  1996,  1155 
  • 5d Knölker H.-J. J. Prakt. Chem.  1997,  339:  304 
    Suche in Google Scholar
  • 5e Knölker H.-J. Foitzik N. Schmitt O. Tetrahedron Lett.  1999,  40:  3557 
    Suche in Google Scholar
  • 5f Knölker H.-J. Baum E. Graf R. Jones PG. Spiess O. Angew. Chem. Int. Ed.  1999,  38:  2583 
    Suche in Google Scholar
  • 6a Knölker H.-J. Foitzik N. Goesmann H. Graf R. Jones PG. Wanzl G. Chem. Eur. J.  1997,  3:  538 
    Suche in Google Scholar
  • 6b Knölker H.-J. Foitzik N. Gabler C. Graf R. Synthesis  1999,  145 
  • 7a Judd WR. Ban S. Aubé J. J. Am. Chem. Soc.  2006,  128:  13736 
    Suche in Google Scholar
  • 7b Peng Z.-H. Woerpel KA. J. Am. Chem. Soc.  2003,  125:  6018 
    Suche in Google Scholar
  • 7c Nair V. Rajesh C. Dhanya R. Rath NP. Org. Lett.  2002,  4:  953 
    Suche in Google Scholar
  • 7d Roberson CW. Woerpel KA. J. Am. Chem. Soc.  2002,  124:  11342 
    Suche in Google Scholar
  • 7e Akiyama T. Sugano M. Kagoshima H. Tetrahedron Lett.  2001,  42:  3889 
    Suche in Google Scholar
  • 7f Micalizio GC. Roush WR. Org. Lett.  2001,  3:  1949 
    Suche in Google Scholar
  • 7g Isaka M. Williard PG. Nakamura E. Bull. Chem. Soc. Jpn.  1999,  72:  2115 
    Suche in Google Scholar
  • 7h Akiyama T. Hoshi E. Fujiyoshi S. J. Chem. Soc., Perkin Trans. 1  1998,  2121 
  • 7i Akiyama T. Yamanaka M. Tetrahedron Lett.  1998,  39:  7885 
    Suche in Google Scholar
  • 7j Groaning MD. Brengel GP. Meyers AI. J. Org. Chem.  1998,  63:  5517 
    Suche in Google Scholar
  • 7k Brengel GP. Meyers AI. J. Org. Chem.  1996,  61:  3230 
    Suche in Google Scholar
  • 7l Panek JS. Jain NF. J. Org. Chem.  1993,  58:  2345 
    Suche in Google Scholar
  • 7m Danheiser RL. Takahashi T. Bertók B. Dixon BR. Tetrahedron Lett.  1993,  34:  3845 
    Suche in Google Scholar
  • 8a Fleming I. Chemtracts: Org. Chem.  1996,  9:  1 
    Suche in Google Scholar
  • 8b Tamao K. In Advances in Silicon Chemistry   Vol. 3:  JAI Press; Greenwich, CT: 1996.  p.1 
    Suche in Google Scholar
  • 8c Jones GR. Landais Y. Tetrahedron  1996,  52:  7599 
    Suche in Google Scholar
  • 8d Mader MM. Norrby P.-O. J. Am. Chem. Soc.  2001,  123:  1970 
    Suche in Google Scholar
  • 9a Knölker H.-J. Wanzl G. Synlett  1995,  378 
  • 9b Knölker H.-J. Jones PG. Wanzl G. Synlett  1998,  613 
  • 10 Part 17 of Cycloadditions of Allylsilanes. For part 16, see: Knölker H.-J. Baum G. Schmitt O. Wanzl G. Chem. Commun.  1999,  1737 
  • 11 Paquette LA. Leone-Bay A. J. Am. Chem. Soc.  1983,  105:  7352 
    Suche in Google Scholar
  • 14a Griffith WP. Ley SV. Aldrichimica Acta  1990,  23:  13 
    Suche in Google Scholar
  • 14b Ley SV. Norman J. Griffith WP. Marsden SP. Synthesis  1994,  639 
  • 15a Corey EJ. Suggs JW. Tetrahedron Lett.  1975,  2647 
  • 15b Piancatelli G. Scettri A. D’Auria M. Synthesis  1982,  245 
  • 16 Herscovici J. Egron M.-J. Antonakis K. J. Chem. Soc., Perkin Trans. 1  1982,  1967 
  • 17 Morita Y. Suzuki M. Noyori R. J. Org. Chem.  1989,  54:  1785 
    Suche in Google Scholar
  • 19 Winterfeldt E. Synthesis  1975,  617 
12

Characteristic Spectroscopic Data of the Triquinanes 7, 11-14 and 1
Compound anti-7: colorless oil. 13C NMR and DEPT (125 MHz, CDCl3): δ = 18.57 (C), 24.55 (CH3), 25.35 (CH), 27.34 (CH3), 27.87 (CH3), 28.47 (3 CH3), 29.45 (CH2), 35.57 (CH2), 38.36 (CH2), 40.01 (CH2), 44.94 (C), 47.21 (C), 48.03 (CH2), 55.03 (CH), 70.98 (C), 127.28 (2 CH), 127.36 (2 CH), 128.88 (2 CH), 134.32 (C), 134.44 (C), 136.54 (2 CH), 136.56 (2 CH), 229.55 (C=O).
syn-7: colorless oil. 13C NMR and DEPT (125 MHz, CDCl3): δ = 18.04 (C), 22.31 (CH3), 26.37 (CH3), 26.89 (CH2), 28.47 (3 CH3), 28.60 (CH), 29.83 (CH3), 30.64 (CH2), 31.19 (CH2), 41.75 (CH2), 45.16 (C), 45.56 (CH), 46.70 (CH2), 48.90 (C), 68.11 (C), 127.45 (2 CH), 134.82 (C), 135.29 (C), 136.13 (2 CH), 136.25 (2 CH), 136.54 (2 CH), 136.56 (2 CH), 223.41 (C=O).
Compound 11: colorless oil. 13C NMR and DEPT (125 MHz, CDCl3): δ = 25.59 (CH3), 27.13 (2 CH3), 31.07 (CH2), 41.69 (CH2), 43.49 (CH2), 43.92 (CH2), 45.61 (C), 46.52 (CH), 47.35 (C), 49.76 (CH2), 66.86 (C), 217.06 (C=O), 225.86 (C=O).
Compound 12: colorless oil. 13C NMR and DEPT (125 MHz, CDCl3): δ = 14.90 (CH3), 25.84 (CH3), 26.25 (CH3), 26.99 (CH3), 29.04 (CH2), 42.31 (CH2), 44.07 (CH2), 46.04 (C), 46.26 (C), 49.10 (CH), 50.18 (CH2), 55.85 (CH), 64.41 (C), 218.76 (C=O), 226.94 (C=O).
Compound 13: colorless crystals, mp 84 °C. 13C NMR and DEPT (125 MHz, CDCl3): δ = 13.69 (CH3), 25.27 (CH3), 25.74 (CH2), 26.78 (CH2), 27.11 (CH3), 27.52 (CH3), 28.02 (CH2), 28.79 (CH2), 40.29 (CH2), 44.29 (C), 47.14 (CH2), 47.80 (C), 49.16 (CH2), 52.47 (CH), 58.69 (CH), 60.77 (C), 68.16 (C), 225.62 (C=O). Anal. Calcd (%) for C18H28OS2: C, 66.61; H, 8.70; S, 19.76. Found: C, 66.60; H, 8.48; S, 19.68.
Compound 14: colorless oil. 13C NMR and DEPT (125 MHz, CDCl3): δ = 18.83 (CH3), 24.60 (CH3), 27.38 (CH3), 27.70 (CH3), 28.81 (CH2), 31.71 (CH2), 36.58 (CH2), 40.83 (CH2), 43.26 (CH), 44.97 (C), 47.62 (C), 48.37 (CH2), 61.17 (CH), 70.67 (C), 229.19 (C=O).
(±)-Cameroonanol [(±)-1]: colorless crystals, mp 42-45 °C. IR (ATR): ν = 3604, 3479, 2929, 2864, 1458, 1374, 1242, 1163, 1077, 1051, 997, 976, 910, 782, 667 cm-1. 1H NMR (500 MHz, CDCl3): δ = 0.90 (s, 3 H), 0.96 (s, 3 H), 0.99 (d, J = 6.6 Hz, 3 H), 1.03 (s, 3 H), 1.18-1.27 (m, 1 H), 1.30-1.34 (m, 1 H), 1.38-1.45 (m, 3 H), 1.50-1.67 (m, 5 H), 1.73-1.81 (m, 1 H), 1.90 (t, J = 8.2 Hz, 1 H), 3.68 (br s, 1 H). 13C NMR and DEPT (125 MHz, CDCl3): δ = 19.37 (CH3), 23.79 (CH3), 25.67 (CH3), 28.99 (CH2), 32.45 (CH3), 35.33 (CH2), 36.11 (CH2), 38.64 (C), 39.97 (CH2), 43.82 (CH), 47.56 (C), 51.36 (CH), 52.60 (CH2), 67.10 (C), 89.71 (CH). MS (EI): m/z (%) = 222 (7), 207 (11), 204 (39), 189 (27), 176 (13), 166 (40), 148 (50), 135 (100), 124 (49), 109 (24), 96 (41), 95 (36), 93 (29), 81 (32). HRMS: m/z calcd for C15H26O: 222.1984; found: 222.1971. Anal. Calcd (%) for C15H26O: C, 81.02; H, 11.79. Found: C, 81.05; H, 11.74.
(±)-epi-Cameroonanol [(±)-epi-1]: colorless oil. 1H NMR (500 MHz, CDCl3): δ = 0.81 (s, 3 H), 0.91 (d, J = 6.6 Hz, 3 H), 0.96 (s, 3 H), 1.03 (s, 3 H), 1.19-1.88 (m, 12 H), 3.35 (br s, 1 H). 13C NMR and DEPT (125 MHz, CDCl3): δ = 19.01 (CH3), 21.49 (CH3), 25.66 (CH2), 26.40 (CH2), 28.44 (CH3), 28.51 (CH3), 36.75 (CH2), 38.13 (CH), 41.75 (C), 43.48 (CH2), 48.36 (C), 52.71 (CH2), 62.73 (CH), 65.70 (C), 88.24 (CH). GC-MS (EI): m/z (%) = 222 (8), 204 (41), 189 (27), 175 (34), 166 (55), 148 (42), 135 (100), 124 (46), 119 (37), 107 (40), 95 (40), 93 (40), 91 (53), 79 (45).

13

Crystal Data for anti -10
C18H32O3Si, crystal size: 0.51 × 0.47 × 0.08 mm3, M r = 324.53 g mol-1, triclinic, space group P1bar, λ = 0.71073 Å, a = 12.186 (3) Å, b = 15.114 (1) Å, c = 16.730 (4) Å, α = 103.50 (1)°, β = 95.17 (2)°, γ = 104.16 (1)°, V = 2869.5 (10) Å3, Z = 6, ρ calcd = 1.127 g cm-3, µ = 0.133 mm-1, T = 198 (2) K, θ range = 3.52-22.50°; reflections collected: 43390, independent: 7450 (R int = 0.0522). The structure was solved by direct methods and refined by full-matrix least-squares on F 2; R 1 = 0.0407, wR 2 = 0.1006 [I > 2σ(I)]; maximal residual electron density: 0.464 e Å-3. CCDC 636590 contains the supplementary crystallographic data for this structure. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

18

Crystal Data for 13
C18H28OS2, crystal size: 0.46 × 0.34 × 0.28 mm3, M r = 324.52 g mol-1, triclinic, space group P1bar, λ = 0.71073 Å, a = 7.486 (2) Å, b = 9.117 (2) Å, c = 13.246 (3) Å, α = 85.58 (3)°, β = 77.34 (3)°, γ = 87.08 (3)°, V = 878.9 (4) Å3, Z = 2, ρ calcd = 1.226 g cm-3, µ = 0.301 mm-1, T = 198 (2) K, θ range = 3.52-25.41°; reflections collected: 11484, independent: 3126 (R int = 0.0295). The structure was solved by direct methods and refined by full-matrix least-squares on F 2; R 1 = 0.0351, wR 2 = 0.0769 [I > 2σ(I)]; maximal residual electron density: 0.273 e Å-3. CCDC 636591 contains the supplementary crystallographic data for this structure. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.