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38849131544
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Typical Procedure for the Preparation of 2: To a solution of bicyclic vinylidenecyclopropanes (0.5 mmol) in anhyd CH2Cl 2 (3 mL) under N2 was added TiCl4 (28.4 mg, 0.15 mmol) under a nitrogen atmosphere. The mixture was stirred at r.t. for 2 h. After the reaction was complete, the mixture was concentrated and the residue was purified by flash chromatography to afford medium- and large-size naphthalenacarbocycles 2. Selected spectral data for 2h: 1H NMR (400 MHz, CDCl3, δ, 8.07 (d, J, 8.0 Hz, 1 H, 7.87 (d, J, 8.4 Hz, 1 H, 7.42-7.53 (m, 5 H, 7.36-7.42 (m, 1 H, 7.30-7.36 (m, 1 H, 7.25 (s, 1 H, 3.00-3.09 (m, 2 H, 2.70-2.80 (m, 2 H, 1.74-1.89 (m, 4 H, 1.64-1.73 (m, 2 H, 1.48-1.64 (m, 6 H, 1.34-1.48 (m, 6 H, 13C NMR 100 MHz, CDCl3, δ, 23.2, 23.4, 24.5, 24.6, 26.4, 26.6, 26.9, 27.0, 27.1, 27.8, 32.3, 123.9, 124.5, 125.6, 126.6, 126.9, 128.1
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32: 356.2504; found: 356.2512.
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34
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38849145263
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Spectral data for 2i: 1H NMR (400 MHz, CDCl 3, 7.33-7.41 (m, 3 H, 7.27-7.32 (m, 7 H, 6.42 (s, 1 H, 5.57 (t, J, 2.6 Hz, 1 H, 4.24 (d, J, 2.2 Hz, 1 H, 4.17 (dd, J1, 3.7 Hz, J2, 18.0 Hz, 1 H, 4.08 (dd, J1, 1.8 Hz, J2, 17.8 Hz, 1 H, 3.98 (dd, J1, 2.9 Hz, J2, 12.4 Hz, 1 H, 3.87 (dd, J1, 3.0 Hz, J2, 12.4 Hz, 1 H, 13C NMR (100 MHz, CDCl3, δ, 54.0, 65.5, 70.0, 125.1, 127.4, 127.5, 127.6, 128.1, 128.3, 129.8, 132.7, 140.0, 142.5, 143.9. IR (film, 3056, 3024, 2925, 2852, 1658, 1598, 1491, 1445, 1380, 1135, 1080, 758, 700 cm-1. MS (70 eV, EI, m/z, 296 [M, 231 100
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+], 231 (100).
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