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DOI: 10.1055/s-2007-1000844
A Facile Access to Medium- and Large-Size Naphthalenacarbocycles via Lewis Acid Mediated Ring-Expansion Reaction of Bicyclic Vinylidenecyclopropanes
Publication History
Publication Date:
21 December 2007 (online)
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Abstract
Ring-expansion reactions of bicyclic vinylidenecyclopropanes in the presence of Lewis acid was investigated, providing an efficient method for the synthesis of naphthalenes with annulated carbocycles of various ring sizes in good to excellent yields under mild conditions.
Key words
bicyclic vinylidenecyclopropanes - ring expansion - Lewis acids
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References and Notes
Typical Procedure for the Preparation of 2: To a solution of bicyclic vinylidenecyclopropanes (0.5 mmol) in anhyd CH2Cl2 (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, 129.8, 130.2, 130.6, 132.8, 135.1, 137.4, 138.2, 141.1. IR (KBr): 2929, 2856, 1461, 1383, 762, 707 cm-1. MS (70 eV, EI): m/z = 356 [M+], 356 (100). HRMS (EI): m/z [M+] calcd for C27H32: 356.2504; found: 356.2512.
12Spectral data for 2i: 1H NMR (400 MHz, CDCl3): = 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, J 1 = 3.7 Hz, J 2 = 18.0 Hz, 1 H), 4.08 (dd, J 1 = 1.8 Hz, J 2 = 17.8 Hz, 1 H), 3.98 (dd, J 1 = 2.9 Hz, J 2 = 12.4 Hz, 1 H), 3.87 (dd, J 1 = 3.0 Hz, J 2 = 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).