Stereoselective Total Synthesis of the Sesquiterpene (±)-Cameroonanol

Arndt W. Schmidt; Thomas Olpp; Sören Schmid; Sigrid Goutal; Anne Jäger; Hans-Joachim Knölker

doi:10.1055/s-2007-982535

LETTER

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;

Abstract

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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

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References and Notes

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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).

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.

<A NAME="RG09807ST-14A">14a</A> Griffith WP. Ley SV. Aldrichimica Acta 1990, 23: 13

<A NAME="RG09807ST-14B">14b</A> Ley SV. Norman J. Griffith WP. Marsden SP. Synthesis 1994, 639

<A NAME="RG09807ST-15A">15a</A> Corey EJ. Suggs JW. Tetrahedron Lett. 1975, 2647

<A NAME="RG09807ST-15B">15b</A> Piancatelli G. Scettri A. D’Auria M. Synthesis 1982, 245

<A NAME="RG09807ST-16">16</A> Herscovici J. Egron M.-J. Antonakis K. J. Chem. Soc., Perkin Trans. 1 1982, 1967

<A NAME="RG09807ST-17">17</A> Morita Y. Suzuki M. Noyori R. J. Org. Chem. 1989, 54: 1785

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.

<A NAME="RG09807ST-19">19</A> Winterfeldt E. Synthesis 1975, 617