A Facile Access to Medium- and Large-Size Naphthalenacarbocycles via Lewis Acid Mediated Ring-Expansion Reaction of Bicyclic Vinylidenecyclopropanes

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

References and Notes

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11

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.

12

Spectral 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).