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17 Characteristic Spectroscopic Data of 10, 11, (±)-1, and (±)-2:
Compound 10: colorless crystals, mp 112 °C. 13C NMR and DEPT (125 MHz, CDCl3): δ = 18.60 (C), 19.83 (CH3), 21.64 (CH), 23.23 (CH2), 23.72 (CH3), 28.47 (3 CH3), 35.46 (CH2), 40.17 (CH2), 43.21 (CH2), 44.92 (CH2), 45.83 (C), 53.14 (CH2), 59.61 (C), 62.43 (C), 127.48 (4 CH), 129.11 (2 CH), 133.76 (C), 134.12 (C), 136.47 (2 CH), 136.53 (2 CH), 223.74 (C=O). Anal. Calcd (%) for C29H38OSi: C, 80.87; H, 8.89. Found: C, 80.64; H, 8.26.
Compound 11: colorless oil. 13C NMR and DEPT (125 MHz, CDCl3): δ = 21.12 (CH3), 22.96 (CH2), 23.00 (CH3), 35.58 (CH2), 41.29 (CH2), 45.48 (CH2), 46.23 (C), 49.07 (CH2), 50.19 (CH2), 57.46 (C), 61.44 (C), 71.76 (CH), 223.43 (C=O).
(±)-β-Isocomene [(±)-1]: colorless crystals, mp 76-82 °C. IR (ATR): ν = 3073, 2925, 2869, 2854, 1655, 1460, 1376, 1260, 1106, 1024, 878 cm-1. 1H NMR (500 MHz, CD2Cl2): δ = 0.92 (d, J = 7.0 Hz, 3 H), 0.99 (s, 3 H), 1.10 (s, 3 H), 1.22-1.68 (m, 10 H), 2.00 (m, 1 H), 2.10 (d, J = 14.4 Hz, 1 H), 2.34 (dt, J = 14.4, 2.4 Hz, 1 H), 4.60 (m, 1 H), 4.63 (m, 1 H). 13C NMR and DEPT (125 MHz, CD2Cl2): δ = 18.08 (CH3), 23.53 (CH3), 24.27 (CH3), 24.33 (CH2), 30.55 (CH2), 34.87 (CH2), 40.83 (CH), 41.95 (CH2), 43.15 (CH2), 48.23 (CH2), 49.68 (C), 55.14 (C), 67.01 (C), 100.79 (CH2), 162.76 (C). MS (EI): m/z (%) = 204 (21) [M+], 189 (68), 175 (12), 162 (15), 161 (35), 149 (22), 148 (29), 147 (49), 134 (28), 133 (42), 122 (29), 121 (44), 120 (31), 119 (40), 109 (68), 108 (100), 107 (60). Anal. Calcd (%): for C15H24O: C, 88.16; H, 11.84. Found: C, 88.27; H, 11.98.
(±)-Isocomene [(±)-2]: colorless oil. IR (ATR): ν = 3020, 2927, 2866, 2853, 1672, 1458, 1443, 1375, 1002, 940, 845 cm-1. 1H NMR (500 MHz, CDCl3): δ = 0.85 (d, J = 7.2 Hz, 3 H), 1.026 (s, 3 H), 1.030 (s, 3 H), 1.14-1.43 (m, 5 H), 1.48-1.58 (m, 4 H), 1.55 (d, J = 1.3 Hz, 3 H), 1.70-1.73 (m, 1 H), 1.99 (m, 1 H), 4.85 (m, 1 H). 13C NMR and DEPT (125 MHz, CDCl3): δ = 13.00 (CH3), 17.27 (CH3), 23.16 (CH3), 23.71 (CH3), 24.01 (CH2), 31.91 (CH2), 33.62 (CH2), 37.22 (CH2), 39.88 (CH), 42.60 (CH2), 56.61 (C), 59.86 (C), 63.75 (C), 132.66 (CH), 142.81 (C). MS (EI): m/z (%) = 204 (10) [M+], 189 (16), 175 (7), 162 (100), 161 (17), 147 (49), 134 (18), 133 (19), 119 (31), 105 (20), 91 (18). Anal. Calcd (%) for C15H24O: C, 88.16; H, 11.84. Found: C, 88.20; H, 11.80.
18 Crystal data for 10: C29H38OSi, crystal size: 0.60 × 0.40 × 0.40 mm3, M
r = 430.68 g mol-1, monoclinic, space group P21/c, λ = 0.71073 Å, a = 13.4071(14), b = 12.1653(9), c = 16.2492(17) Å, β = 109.414(11)°, V = 2499.6(4) Å3, Z = 4, ρ
calcd = 1.144 g cm-3, µ = 0.112 mm-1, T = 200(2) K, θ range = 2.14°-25.85°; reflections collected: 18979, independent: 4787 (R
int = 0.0393). The structure was solved by direct methods and refined by full-matrix least-squares on F
2; R
1 = 0.0481, wR
2 = 0.1275 [I > 2σ(I)]; maximal residual electron density: 0.424 e Å-3. CCDC 646230 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.
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22 Ratio of compound 15/monoalkylated isomer 1/monoalkylated isomer 2/dialkylated product 1/dialkylated product 2 = 78.2:14.0:3.6:2.2:2.0.