PDF herunterladen
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;
Weitere Informationen

Publikationsverlauf

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

    Lizenzen und Reprints Alle Artikel dieser Rubrik

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